Treatment liquid and pattern forming method

ABSTRACT

An object of the present invention is to provide a treatment liquid for patterning a resist film and a pattern forming method, each of which can simultaneously suppress the occurrence of pattern collapse in a resist L/S pattern and the occurrence of omission failure in a resist C/H pattern.The treatment liquid of the present invention is a treatment liquid for patterning a resist film, which is used for subjecting a resist film obtained from an actinic ray-sensitive or radiation-sensitive resin composition to at least one of development or washing, and contains an organic solvent, in which the treatment liquid contains a first organic solvent having a relative dielectric constant of 4.0 or less and a second organic solvent having a relative dielectric constant of 6.0 or more.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of PCT International Application No.PCT/JP2016/078168 filed on Sep. 26, 2016, which claims priority under 35U.S.C. § 119(a) to Japanese Patent Application No. 2015-195125 filed onSep. 30, 2015 and Japanese Patent Application No. 2016-096436 filed onMay 12, 2016. Each of the above applications is hereby expresslyincorporated by reference, in its entirety, into the presentapplication.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a treatment liquid for patterning aresist film and a pattern forming method.

More specifically, the present invention relates to a treatment liquidwhich is used in a process for manufacturing a semiconductor such as anintegrated circuit (IC), the manufacture of a circuit board for a liquidcrystal, a thermal head, or the like, and other lithographic processesfor photofabrication processes, and the like, and a pattern formingmethod.

2. Description of the Related Art

In the related art, in a process for manufacturing a semiconductordevice such as an integrated circuit (IC) and a large scale integratedcircuit (LSI), microfabrication by lithography using a photoresistcomposition has been carried out. In recent years, ultrafine patternformation in a sub-micron region and a quarter-micron region has beenrequired, in accordance with realization of high integration ofintegrated circuits. In such a circumstance, exposure wavelength has atendency to become shorter, such as from a g-ray to an i-ray, andfurther to KrF excimer laser light. Further, development of lithographyusing electron beams, X-rays, or extreme ultraviolet (EUV) light, inaddition to the excimer laser light, is also now progressing.

In such the lithography, after forming a film using a photoresistcomposition (also called an actinic ray-sensitive or radiation-sensitiveresin composition or a chemically amplified resist composition), theobtained film has been developed with a developer, or the developed filmhas been rinsed with a rinsing liquid.

For example, JP2012-181523A discloses that an organic treatment liquidcontaining a mixture of a first organic solvent and a second organicsolvent, selected from a ketone-based solvent and an ester-basedsolvent, is used as a developer.

SUMMARY OF THE INVENTION

In recent years, in accordance with realization of high integration ofintegrated circuits, formation of a fine pattern using a photoresistcomposition (actinic ray-sensitive or radiation-sensitive resincomposition) has been required. In such the formation of a fine pattern,the following problems occur as the patterns become finer, and thus, theperformance of the resist pattern is easily deteriorated. That is, in anL/S pattern (line space pattern), as the pattern becomes finer, adistance between the patterns becomes shorter, resulting in generationof a large capillary force, and thus, “pattern collapse” easily occurs.On the other hand, in a C/H pattern (contact hole pattern), as thepattern becomes finer, a pore diameter of the contact hole is smaller,and thus, “omission failure”, such as failures in which the edges of theholes are connected to each other or the holes do not open at all,easily occurs. The developer and the rinsing liquid are not limited interms of the types of patterns, such as an L/S pattern and a C/Hpattern, and have been required to exhibit good performance, and adeveloper and a rinsing liquid, capable of simultaneously addressing theproblems of the occurrences of pattern collapse and omission failure,have been required.

However, a developer and a rinsing liquid, each of which cansimultaneously suppress the occurrences of pattern collapse and omissionfailure in fine patterns, have yet not been known.

The present invention has been made in view of the above viewpoints, andhas an object to provide a treatment liquid for patterning a resist filmand a pattern forming method, each of which can simultaneously suppressthe occurrence of pattern collapse in a resist L/S pattern and theoccurrence of omission failure in a resist C/H pattern.

The present inventors have conducted extensive studies on the aboveobject, and as a result, have discovered that a desired effect isobtained by using an organic treatment liquid including a combination ofat least two organic solvents having relative dielectric constants indifferent specific ranges.

More specifically, the present inventors have discovered that the objectcan be accomplished by the following configurations.

(1) A treatment liquid for patterning a resist film,

used for subjecting a resist film obtained from an actinic ray-sensitiveor radiation-sensitive resin composition to at least one of developmentor washing, and

containing an organic solvent,

in which the treatment liquid contains a first organic solvent having arelative dielectric constant of 4.0 or less and a second organic solventhaving a relative dielectric constant of 6.0 or more.

(2) The treatment liquid as described in (1),

in which the treatment liquid is a rinsing liquid.

(3) The treatment liquid as described in (2),

in which the first organic solvent includes a hydrocarbon-based solvent.

(4) The treatment liquid as described in (3),

in which the first organic solvent includes a hydrocarbon-based solventhaving 10 or more carbon atoms.

(5) The treatment liquid as described in (3) or (4),

in which the hydrocarbon-based solvent includes undecane.

(6) The treatment liquid as described in any one of (1) to (5),

in which the second organic solvent includes a ketone-based solvent.

(7) The treatment liquid as described in (6),

in which the ketone-based solvent includes an acyclic ketone.

(8) A pattern forming method comprising:

a resist film forming step of forming a resist film using an actinicray-sensitive or radiation-sensitive resin composition;

an exposing step of exposing the resist film; and

a treating step of treating the exposed resist film with the treatmentliquid as described in any one of (1) to (7).

(9) The pattern forming method as described in (8),

in which the treating step includes:

a developing step of carrying out development with a developer; and

a rinsing step of carrying out washing with a rinsing liquid, and

the rinsing liquid is the treatment liquid as described in any one of(1) to (7).

(10) The pattern forming method as described in (9),

in which the developer includes an ester-based solvent.

(11) The pattern forming method as described in (10),

in which the ester-based solvent is a solvent including at least oneselected from the group consisting of butyl acetate, amyl acetate,isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexylacetate, pentyl propionate, hexyl propionate, heptyl propionate, butylbutanoate, and butyl isobutanoate.

According to the present invention, it is possible to provide atreatment liquid for patterning a resist film and a pattern formingmethod, each of which can simultaneously suppress the occurrence ofpattern collapse in a resist L/S pattern and the occurrence of omissionfailure in a resist C/H pattern.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[Treatment Liquid]

The treatment liquid of the present invention is a treatment liquid forpatterning a resist film, which is used for subjecting a resist filmobtained from an actinic ray-sensitive or radiation-sensitive resincomposition to at least one of development or washing, and contains anorganic solvent. The treatment liquid of the present invention includesa first organic solvent having a relative dielectric constant of 4.0 orless and a second organic solvent having a relative dielectric constantof 6.0 or more.

With the treatment liquid of the present invention, the occurrence ofpattern collapse in a resist L/S pattern and the occurrence of omissionfailure in a resist C/H pattern can be simultaneously suppressed.Details of the reason therefor are still not clear, but are presumed tobe as follows.

It is generally known that as the affinity of a developer and a rinsingliquid to a resist pattern is higher, it is excessively easy for thedeveloper and the rinsing liquid to permeate into the pattern, whichcauses the swelling of the pattern. The swelling of the patternexcessively reduces a distance between the patterns with respect to anoriginal pattern latent image, and as a result, a capillary force isfurther increased. With regard to this problem, it is presumed that byusing a first organic solvent having a relative dielectric constant of4.0 or less, excessive penetration of the resist and the treatmentliquid of the present invention, that is, the swelling, can besuppressed, and thus, the occurrence of pattern collapse in a resist L/Spattern can be suppressed.

On the other hand, omission failure in a C/H pattern is a problem whichis particularly easily manifested with organic solvent development. Thatis, it is thought that due to an effect of a photoacid generator (PAG)or the like, unevenly deposited on the surface, a deprotection amount isslightly larger than that of a bulk layer, and thus, the surface layerof a resist film with relatively high polarity is not dissolved due toan insufficient dissolution contrast of organic solvent development. Itis presumed that the treatment liquid of the present invention canpenetrate into the surface layer of a resist film with relatively highpolarity as described above by incorporation of a second organic solventhaving a relative dielectric constant of 6.0 or more, and thus, it ispossible to make the solubilities of the bulk and the film surface layerapproximate to each other, and thus to suppress the lack of thedissolution of the surface layer, that is, the omission failure of C/H.

As described above, the above-mentioned treatment liquid used as adeveloper and/or a rinsing liquid can simultaneously suppress theoccurrence of pattern collapse in a resist L/S pattern and theoccurrence of omission failure in a resist C/H pattern by incorporationof at least two organic solvents having different relative dielectricconstants.

In addition, particularly as a treatment liquid used in a step to becarried out later, a treatment liquid including a first organic solventhaving a relative dielectric constant of 4.0 or less and a secondorganic solvent having a relative dielectric constant of 6.0 or more ispreferably used, and that is, the treatment liquid of the presentinvention is preferably used in the rinsing liquid.

Furthermore, as the relative dielectric constant of the presentinvention, the relative dielectric constant (usually a value at atemperature of 20° C.) described in “Handbook of Organic SolventProperties, Ian M. Smallwood, 1996, Elsevier” and “CRC Handbook ofChemistry and Physics, 96th Edition, William M. Haynes, 2015, CRC Press”is used.

The treatment liquid of the present invention is typically used as adeveloper and/or a rinsing liquid. The treatment liquid contains anorganic solvent, and preferably contains an antioxidant and/or asurfactant.

Hereinafter, the organic solvent will be first described, and theantioxidant and the surfactant which can be included in the treatmentliquid will be then described.

The treatment liquid in the present invention includes a first organicsolvent having a relative dielectric constant of 4.0 or less and asecond organic solvent having a relative dielectric constant of 6.0 ormore.

In a case where the relative dielectric constant of the first organicsolvent is more than 4.0, the affinity to the resist film is extremelyhigh, and the developer and the rinsing liquid excessively easilypenetrate into the resist film pattern, which causes the swelling of thepattern. Further, in a case where the relative dielectric constant ofthe second organic solvent is less than 6.0, the solubility of theoutermost layer of the resist film with a relatively high polarity withrespect to the bulk layer as described above is insufficient, and thus,the omission failure of C/H occurs.

<First Organic Solvent Having Relative Dielectric Constant of 4.0 orLess>

The first organic solvent having a relative dielectric constant of 4.0or less is selected from various organic solvents, but for example, asolvent such as a hydrocarbon-based solvent, an ether-based solvent, andan ester-based solvent can be used. The lower limit of the relativedielectric constant of the first organic solvent is not particularlylimited, but is, for example, 1.6 or more.

Among these, from the viewpoint that the effect of the present inventionis superior, a hydrocarbon-based solvent or an ether-based solventhaving a relative dielectric constant of 4.0 or less is preferable, anda hydrocarbon-based solvent having a relative dielectric constant of 4.0or less is more preferable.

In addition, the relative dielectric constant of the first organicsolvent is preferably 3.0 or less, and more preferably 2.5 or less. Bysetting the relative dielectric constant to this range, the omissionfailure of C/H can also be further improved.

Examples of the hydrocarbon-based solvent are shown below. The numbersin the parentheses represent relative dielectric constants.

Aliphatic hydrocarbon-based solvents such as pentane (1.8), hexane(1.9), heptane (1.9), octane (2.0), nonane (2.0), decane (2.0), undecane(2.0), dodecane (2.0), hexadecane (2.1), 2,2,4-trimethylpentane (1.9),2-methylhexane (1.9), isohexane (1.9), isooctane (2.0), isodecane (2.0),isododecane (2.1), and isohexadecane (2.1); and unsaturatedhydrocarbon-based solvents such as octene (2.1) and nonene (2.2), and

aliphatic cyclic hydrocarbon-based solvents such as cyclohexane (1.9),cycloheptane (2.1), and cyclooctane (2.1); and aromatichydrocarbon-based solvents such as toluene (2.4), xylene (2.6),propylbenzene (2.4), dimethylbenzene (2.6), and trimethylbenzene (2.7).

The number of the double bonds and the triple bonds contained in theunsaturated hydrocarbon solvent is not particularly limited, and thedouble bonds and the triple bonds may be contained in any of positionsin the hydrocarbon chain (provided that the above-mentioned valuesrepresent cases where the first position of the carbon atoms issubstituted with a double bond). Further, in a case where theunsaturated hydrocarbon solvent has a double bond, cis isomers and transisomers may coexist.

The aliphatic hydrocarbon-based solvent which is a hydrocarbon-basedsolvent may be a mixture of compounds having the same number of carbonatoms and different structures as long as the relative dielectricconstants are within the ranges. For example, in a case where decane isused as the aliphatic hydrocarbon-based solvent, 2-methylnonane (2.0),2,2-dimethyloctane (2.0), 4-ethyloctane (2.0), and the like, which arecompounds having the same number of carbon atoms and differentstructures, may be included in the aliphatic hydrocarbon-based solvent.

Furthermore, one kind or a plurality of kinds of the compounds havingthe same number of carbon atoms and different structures may beincluded.

The upper limit value of the number of carbon atoms of the aliphatichydrocarbon-based solvent is not particularly limited, but is may be,for example, 16 or less, preferably 14 or less, and more preferably 12or less.

Among the aliphatic hydrocarbon-based solvents, decane (2.0), undecane(2.0), or isodecane (2.0) is particularly preferable, and undecane (2.0)is the most preferable.

Examples of the ether solvent are shown below. The numbers in theparentheses represent relative dielectric constants.

For example, acyclic aliphatic ether-based solvents such as dipentylether (3.1), dibutyl ether (3.1), dipropyl ether (3.4), and ethyl pentylether (3.6), and

acyclic aliphatic ether-based solvents having a branched alkyl group,such as di-tert-butyl ether (3.1) and diisopropyl ether (4.0).

It is preferable that the treatment liquid of the present inventionincludes a hydrocarbon-based solvent having 10 or more carbon atoms asthe first organic solvent, from the viewpoint of an effect that theoccurrence of pattern collapse in a resist L/S pattern and theoccurrence of omission failure in a resist C/H pattern can besimultaneously suppressed (hereinafter also referred to as “the effectof the present invention”) is superior. Among these, as thehydrocarbon-based solvent having 10 or more carbon atoms, an aliphatichydrocarbon-based solvent having 10 or more carbon atoms is morepreferably included, decane (2.0), undecane (2.0), or isodecane (2.0) isstill more preferably included, and undecane (2.0) is most preferablyincluded.

<Second Organic Solvent Having Relative Dielectric Constant of 6.0 orMore>

The second organic solvent having a relative dielectric constant of 6.0or more is selected from various organic solvents, but for example, aketone-based solvent, an ester-based solvent, an alcohol-based solvent,an amide-based solvent, an ether-based solvent, or a hydrocarbon-basedsolvent can be used. The upper limit of the relative dielectric constantof the second organic solvent is not particularly limited, but is, forexample, 32.5 or less.

Among these, from the viewpoint that the effect of the present inventionis superior, a ketone-based solvent or an ester-based solvent having arelative dielectric constant of 6.0 or more is preferable and aketone-based solvent having a relative dielectric constant of 6.0 ormore is more preferable.

In addition, the relative dielectric constant of the second organicsolvent is preferably from 6 to 20, more preferably from 6 to 14, andmost preferably from 6 to 10. By setting the relative dielectricconstant to these ranges, the pattern collapse of L/S can also befurther improved.

Moreover, in the present invention, the ester-based solvent refers to asolvent having an ester group in a molecule thereof, the ketone-basedsolvent refers to a solvent having a ketone group in a molecule thereof,the alcohol-based solvent refers to a solvent having an alcoholichydroxyl group in a molecule thereof, the amide-based solvent refers toa solvent having an amide group in a molecule thereof, and theether-based solvent refers to a solvent having an ether bond in amolecule thereof. Among these, a solvent having a plurality of kinds offunctional groups in one molecule thereof, but in this case, the solventis intended to correspond to any of solvents including the functionalgroups contained in the above-mentioned solvent. For example, diethyleneglycol monomethyl ether is intended to correspond to any of thealcohol-based solvent and the ether-based solvent among the solvents.

Examples of an organic solvent which can be used as the second organicsolvent are shown below, but the present invention is not limitedthereto. The numbers in the parentheses represent relative dielectricconstants.

Examples of the ester-based solvent include methyl acetate (6.7), ethylacetate (6.0), propyl acetate (6.3), propylene glycol monomethyl etheracetate (PGMEA; alternative name: 1-methoxy-2-acetoxypropane) (8.3),ethylene glycol monoethyl ether acetate (7.6), diethylene glycolmonobutyl ether acetate (7.0), propylene glycol monomethyl ether acetate(8.3), methyl formate (8.5), ethyl formate (8.4), isobutyl formate(6.5), ethyl lactate (13.1), and ethyl acetoacetate (15.9).

Among these, propylene glycol monomethyl ether acetate (PGMEA;alternative name: 1-methoxy-2-acetoxypropane) (8.3) is particularlypreferably used.

Examples of the ketone-based solvent include 2-octanone (10.4),3-octanone (10.4), acetone (21.5), 2-heptanone (12.0), 3-heptanone(12.9), 5-nonanone (10.6), 2,6-dimethyl-4-heptanone (9.9), 4-heptanone(12.6), 2-hexanone (14.6), diisobutyl ketone (9.9),3,3-dimethyl-2-butanone (13.1), cyclohexanone (18.2), cyclopentanone(14.5), 3-methylcyclohexanone (12.4), 4-methylcyclohexanone (12.4),methyl ethyl ketone (18.5), methyl isobutyl ketone (13.1), acetylacetone(23.1), acetophenone (17.4), propylene carbonate (64.9), andγ-butyrolactone (41.7).

Among these, from the viewpoint that the effect of the present inventionis superior, an acyclic ketone-based solvent (acyclic ketone) ispreferable, 2-octanone (10.4), 3-octanone (10.4), 2-heptanone (12.0),3-heptanone (12.9), 4-heptanone (12.6), or diisobutyl ketone (9.9) ispreferable, diisobutyl ketone (9.9) or 2-heptanone (12.0) is morepreferable, and diisobutyl ketone (9.9) is particularly preferable.

As the alcohol-based solvent, for example, alcohols (monovalentalcohols) such as methanol (32.7), ethanol (24.6), 1-propanol (20.3),isopropanol (19.9), 1-butanol (17.8), 2-butanol (17.3),3-methyl-1-butanol (14.7), tert-butyl alcohol (12.5), 1-pentanol (13.9),1-hexanol (13.3), 1-heptanol (12.1), 1-octanol (10.3), 1-decanol (8.1),2-hexanol (13.3), 2-heptanol (9.2), 2-octanol (8.2), 3-heptanol (6.9),4-heptanol (6.2), cyclopentanol (25.0), 2-methyl-2-propanol (10.9),2-methyl-1-propanol (16.7), 4-methyl-2-pentanol (10.4), and cyclohexanol(15.0);

glycol-based solvents such as ethylene glycol (37.7), diethylene glycol(31.7), and triethylene glycol (23.7); and

glycol ether-based solvents containing a hydroxyl group, such aspropylene glycol monomethyl ether (PGME; alternative name:1-methoxy-2-propanol) (12.3), diethylene glycol monobutyl ether (10.2),diethylene glycol monohexyl ether (8.7), diethylene glycol monomethylether (14.8), triethylene glycol monomethyl ether (13.3), andtriethylene glycol monobutyl ether (9.6).

Among these, the glycol ether-based solvents are preferably used.

Examples of the ether-based solvent include tetrahydrofuran (7.6) and2,4,6-trimethyl-1,3,5-trioxane (13.9).

As the amide-based solvent, N-methyl-2-pyrrolidone (32.2),N,N-dimethylacetamide (37.8), N,N-dimethylpropioamide (33.1),N,N-dimethylformamide (36.7), or the like can be used.

Examples of the hydrocarbon-based solvent include aromatichalide-substituted, hydrocarbon-based solvents such asdichloromethylbenzene (6.9), 1,2-dibromobenzene (8.1),1-bromo-2-methoxybenzene (8.9), trifluorobenzene (9.4), and1,2-difluorobenzene (14.3).

The contents of the first organic solvent and the second organic solventare not particularly limited, but the content of the first organicsolvent is usually 10% to 95% by mass, preferably 20% to 95% by mass,more preferably 30% to 80% by mass, and still more preferably 50% to 80%by mass, with respect to the total mass of the treatment liquid.

Furthermore, the content of the second organic solvent is usually 5% to95% by mass, preferably 10% to 70% by mass, and still more preferably10% to 60% by mass, with respect to the total mass of the treatmentliquid.

The mass ratio of the first organic solvent to the second organicsolvent (first organic solvent/second organic solvent) is notparticularly limited, but is preferably 0.25 to 9, and more preferably0.4 to 3.

The treatment liquid of the present invention may include the followingionic liquids. Further, it is noted that in a case where the treatmentliquid includes an ionic liquid, the ionic liquid is not included as anorganic solvent (in other words, not included in the first and secondorganic solvents).

As the ionic liquid, for example, an ionic liquid which has an aromaticion such as a pyridinium ion and an imidazolium ion, an aliphatic aminetype ion such as a trimethyl hexyl ammonium ion, or the like as acation, and an inorganic ion such as NO₃ ⁻, CH₃CO₂ ⁻, BF₆ ⁻, and PF₆ ⁻,a fluorine-containing organic anion such as (CF₃SO₂)₂N⁻, CF₃CO₂ ⁻, orCF₃SO₂ ⁻, and the like as an anion; or a quaternary ammonium salt-basedionic liquid is preferably used.

Examples of commercially available products of the ionic liquid includeIL-P14 and IL-A2 (both manufactured by Koei Chemical Co., Ltd.); andELEGAN SS-100 (manufactured by NOF Corporation) which is a quaternaryammonium salt-based ionic liquid. The ionic liquids are used singly orin combination of two or more kinds thereof.

The content of the ionic liquid is not particularly limited, but in acase where the ionic liquid is contained, the content is preferably 0.5%to 15% by mass, more preferably 1% to 10% by mass, and still morepreferably 1% to 5% by mass, with respect to the total mass of thetreatment liquid.

The treatment liquid of the present invention may include, as an organicsolvent, at least one of each of the first organic solvent having arelative dielectric constant of 4.0 or less and the second organicsolvent having a relative dielectric constant of 6.0 or more asdescribed above, may include a plurality of these organic solvents, ormay also include components to be added, such as other organic solvents(for example, other organic solvents having a relative dielectricconstant not satisfying the above-mentioned range) or ionic liquids.

Furthermore, the treatment liquid may contain water, but in particular,the moisture content in the rinsing liquid is usually 60% by mass orless, preferably 30% by mass or less, still more preferably 10% by massor less, and most preferably 5% by mass or less. By setting the moisturecontent to 60% by mass or less, good rinsing characteristics can beobtained.

As described above, the treatment liquid of the present invention may beused in both of a developer and a rinsing liquid as a washing liquid,but is preferably used in the rinsing liquid.

In a case where the treatment liquid of the present invention is used asthe rinsing liquid in the formation of a pattern, the developer is notparticularly limited, and the treatment liquid of the present invention,or a developer (particularly preferably an ester-based solvent) whichcan be used in combination with the treatment liquid of the presentinvention, which will be described later, is preferably used.

In addition, in a case where the treatment liquid of the presentinvention is used as the developer in the formation of a pattern, therinsing liquid is not particularly limited, and the treatment liquid ofthe present invention, or a rinsing liquid which can be used incombination with the treatment liquid of the present invention, whichwill be described later, is preferably used.

Hereinafter, the developer or the rinsing liquid which can be used incombination with the treatment liquid of the present invention will bedescribed in detail.

Furthermore, an organic solvent used in the developer and an organicsolvent used in the rinsing liquid, which will be shown below, are alsoorganic solvents (organic solvents having relative dielectric constantsnot satisfying the above-mentioned range) which can be used incombination with the first organic solvent and the second organicsolvent, in each of the liquids selected from the developer and therinsing liquid. In other words, the developer can be prepared as aliquid containing both of the first organic solvent and the secondorganic solvent as described above, and an organic solvent used in thedeveloper as shown below. Further, the rinsing liquid can also beprepared as a liquid containing both of the first organic solvent andthe second organic solvent as described above, and an organic solventused in the rinsing liquid as shown below. In addition, among theorganic solvents shown below, an organic solvent having a relativedielectric constant within the above-mentioned range (in other words, anorganic solvent having a relative dielectric constant of 6.0 or more, oran organic solvent having a relative dielectric constant of 4.0 or less)is also included, but it is noted that the organic solvent having arelative dielectric constant within the above-mentioned rangecorresponds to any one of the first organic solvent and the secondorganic solvent. That is, in a case where the developer and the rinsingliquid contain other organic solvents, in addition to the first organicsolvent and the second organic solvent, such the other organic solventsare selected from the organic solvents having a relative dielectricconstant not satisfying the above-mentioned range as described below.

In addition, in a case where the treatment liquid of the presentinvention includes an organic solvent which can be used in combinationwith the first organic solvent and the second organic solvent (anorganic solvent having a relative dielectric constant not satisfying theabove-mentioned range), a content of the organic solvent to be used incombination is preferably 0.5% to 15% by mass, more preferably 1% to 10%by mass, and particularly preferably 1% to 5% by mass, with respect tothe total mass of the treatment liquid.

<Developer which can be Used in Combination with Treatment Liquid ofPresent Invention, or Organic Solvent Used in Developer>

The vapor pressure of the organic solvent used in the developer (in thecase of a mixed solvent, the total vapor pressure) is preferably 5 kPaor less, more preferably 3 kPa or less, and particularly preferably 2kPa or less, at 20° C. By adjusting the vapor pressure of the organicsolvent to 5 kPa or less, the evaporation of the developer on asubstrate or in a developing cup is suppressed, the temperatureuniformity in the wafer surface is improved, and as a result, thedimensional uniformity within a wafer surface is improved.

As the organic solvent used in the developer, various organic solventsare widely used, and for example, solvents such as an ester-basedsolvent, a ketone-based solvent, an alcohol-based solvent, anamide-based solvent, an ether-based solvent, and a hydrocarbon-basedsolvent can be used.

The developer preferably contains, among those, at least one solventselected from a ketone-based solvent, an ester-based solvent, analcohol-based solvent, and an ether-based solvent.

Examples of the ester-based solvent include methyl acetate, ethylacetate, butyl acetate, isobutyl acetate, propyl acetate, isopropylacetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentylacetate), 3-methylbutyl acetate, 2-methylbutyl acetate, 1-methylbutylacetate, hexyl acetate, isohexyl acetate, heptyl acetate, octyl acetate,ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethylether acetate (PGMEA; alternative name: 1-methoxy-2-acetoxy propane),ethylene glycol monoethyl ether acetate, ethylene glycol monopropylether acetate, ethylene glycol monobutyl ether acetate, ethylene glycolmonophenyl ether acetate, diethylene glycol monomethyl ether acetate,diethylene glycol monopropyl ether acetate, diethylene glycol monoethylether acetate, diethylene glycol monophenyl ether acetate, diethyleneglycol monobutyl ether acetate, 2-methoxy butyl acetate, 3-methoxy butylacetate, 4-methoxy butyl acetate, 3-methyl-3-methoxy butyl acetate,3-ethyl-3-methoxy butyl acetate, propylene glycol monoethyl etheracetate, propylene glycol propyl ether acetate, 2-ethoxy butyl acetate,4-ethoxy butyl acetate, 4-propoxy butyl acetate, 2-methoxy pentylacetate, 3-methoxy pentyl acetate, 4-methoxy pentyl acetate,2-methyl-3-methoxy pentyl acetate, 3-methyl-3-methoxy pentyl acetate,3-methyl-4-methoxy pentyl acetate, 4-methyl-4-methoxy pentyl acetate,propylene glycol diacetate, methyl formate, ethyl formate, butylformate, propyl formate, ethyl lactate, butyl lactate, propyl lactate,ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate,ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate,ethyl acetoacetate, methyl propionate, ethyl propionate, propylpropionate, isopropyl propionate, butyl propionate, pentyl propionate,hexyl propionate, heptyl propionate, butyl butanoate, butylisobutanoate, pentyl butanoate, hexyl butanoate, isobutyl isobutanoate,propyl pentanoate, isopropyl pentanoate, butyl pentanoate, pentylpentanoate, ethyl hexanoate, propyl hexanoate, butyl hexanoate, isobutylhexanoate, methyl heptanoate, ethyl heptanoate, propyl heptanoate,cyclohexyl acetate, cycloheptyl acetate, 2-ethylhexyl acetate,cyclopentyl propionate, methyl 2-hydroxypropionate, ethyl2-hydroxypropionate, methyl-3-methoxypropionate,ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, andpropyl-3-methoxypropionate. Among these, butyl acetate, amyl acetate,isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexylacetate, pentyl propionate, hexyl propionate, heptyl propionate, butylbutanoate, or butyl isobutanoate is preferable, and isoamyl acetate orbutyl isobutanoate is particularly preferable.

Examples of the ketone-based solvent include 1-octanone, 2-octanone,1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone,2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone,phenylacetone, methyl ethyl ketone, methyl isobutyl ketone,acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylenecarbonate, γ-butyrolactone, and 2,5-dimethyl-4-hexanone, and amongthese, 2-heptanone is preferable.

Examples of the alcohol-based solvent include alcohols (monovalentalcohols) such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol,2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol,2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol,2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol,3-methyl-3-pentanol, cyclopentanol, 2,3-dimethyl-2-butanol,3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol,3-methyl-2-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol,cyclohexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol,4,5-dimethyl-2-hexanol, 6-methyl-2-heptanol, 7-methyl-2-octanol,8-methyl-2-nonanol, 9-methyl-2-decanol, and 3-methoxy-1-butanol;glycol-based solvents such as ethylene glycol, diethylene glycol, andtriethylene glycol; and glycol ether-based solvents having a hydroxylgroup, such as ethylene glycol monomethyl ether, propylene glycolmonomethyl ether (PGME; alternative name: 1-methoxy-2-propanol),diethylene glycol monomethyl ether, triethylene glycol monoethyl ether,methoxymethylbutanol, ethylene glycol monoethyl ether, ethylene glycolmonopropyl ether, ethylene glycol monobutyl ether, propylene glycolmonoethyl ether, propylene glycol monopropyl ether, propylene glycolmonobutyl ether, and propylene glycol monophenyl ether. Among these, theglycol ether-based solvents are preferably used.

Examples of the ether-based solvent include, in addition to the glycolether-based solvents having a hydroxyl group, glycol ether-basedsolvents having no hydroxyl group, such as propylene glycol dimethylether, propylene glycol diethyl ether, diethylene glycol dimethyl ether,and diethylene glycol diethyl ether; aromatic ether solvents such asanisole and phenetole; and dioxane, tetrahydrofuran, tetrahydropyran,perfluoro-2-butyl tetrahydrofuran, perfluoro tetrahydrofuran,1,4-dioxane, and isopropyl ether. Among these, the glycol ether-basedsolvents or the aromatic ether-based solvents such as anisole arepreferable.

Examples of the amide-based solvent include N-methyl-2-pyrrolidone,N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoricamide, and 1,3-dimethyl-2-imidazolidinone.

Examples of the hydrocarbon-based solvent include aliphatichydrocarbon-based solvents such as pentane, hexane, octane, nonane,decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane,2,2,3-trimethylhexane, perfluorohexane, and perfluoroheptane; andaromatic hydrocarbon-based solvents such as toluene, xylene,ethylbenzene, propylbenzene, 1-methylpropylbenzene,2-methylpropylbenzene, dimethylbenzene, diethylbenzene,ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, anddipropylbenzene.

In addition, as the hydrocarbon-based solvent, an unsaturatedhydrocarbon-based solvent can also be used, and examples thereof includeunsaturated hydrocarbon-based solvents such as octene, nonene, decene,undecene, dodecene, and hexadecene. The number of double bonds or triplebonds contained in the unsaturated hydrocarbon solvent is notparticularly limited, and a hydrocarbon chain may be present at anarbitrary position. In addition, in a case where the unsaturatedhydrocarbon solvent has a double bond, cis isomers and trans isomers maycoexist.

Moreover, the aliphatic hydrocarbon-based solvent which is thehydrocarbon-based solvent may be a mixture of compounds having the samenumber of carbon atoms and different structures. For example, in a casewhere decane is used as the aliphatic hydrocarbon-based solvent, thealiphatic hydrocarbon-based solvent may include compounds having thesame number of carbon atoms and different structures such as2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane.

In addition, as the compounds having the same number of carbon atoms anddifferent structures, one kind may be included, and a plurality of kindsmay be included.

In a case where extreme ultraviolet (EUV) light or electron beams (EB)are used in an exposing step which will be described below, from theviewpoint that the swelling of a resist film can be suppressed, an estersolvent having 6 or more carbon atoms (preferably 6 to 14 carbon atoms,more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10carbon atoms) and having 2 or less heteroatoms is preferably used in thedeveloper.

The heteroatom of the ester-based solvent is an atom other than a carbonatom and a hydrogen atom, and examples thereof include an oxygen atom, anitrogen atom, and a sulfur atom. The number of heteroatoms ispreferably 2 or less.

As a preferred example of the ester-based solvent having 6 or morecarbon atoms and 2 or less heteroatom, at least one selected from butylacetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate,1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexylpropionate, heptyl propionate, butyl butanoate, and butyl isobutanoateis preferable, and isoamyl acetate or butyl isobutanoate is morepreferable.

In a case where extreme ultraviolet (EUV) light or electron beams (EB)are used in an exposing step which will be described below, a mixedsolvent of the ester-based solvent and the hydrocarbon-based solvent ora mixed solvent of the ketone-based solvent and the hydrocarbon solventmay be used, instead of the ester-based solvent having 6 or more carbonatoms and having 2 or less heteroatoms, in the developer. Even in thiscase, the use of the solvents is effective for suppression of theswelling of a resist film.

In a case where the ester-based solvent and the hydrocarbon-basedsolvent are used in combination, it is preferable that isoamyl acetateis used as the ester-based solvent. In addition, it is preferable that asaturated hydrocarbon solvent (for example, octane, nonane, decane,dodecane, undecane, and hexadecane) is used as the hydrocarbon-basedsolvent from the viewpoint of adjusting the solubility of a resist film.

In a case where the ketone-based solvent and the hydrocarbon-basedsolvent are used in combination, it is preferable that diisobutyl ketoneor 2,5-dimethyl-4-hexanone is used as the ketone-based solvent. Inaddition, it is preferable that a saturated hydrocarbon solvent (forexample, octane, nonane, decane, dodecane, undecane, and hexadecane) isused as the hydrocarbon-based solvent from the viewpoint of adjustingthe solubility of a resist film.

In a case where the above-mentioned mixed solvent is used, the contentof the hydrocarbon-based solvent depends on the solvent solubility of aresist film. Therefore, the content of the hydrocarbon-based solvent isnot particularly limited, and may be appropriately adjusted to be anecessary content.

A plurality of the above-mentioned organic solvents may be mixed, or thesolvent may be used in combination with a solvent other than theabove-mentioned solvents or with water. Here, in order to exhibit theeffects of the present invention sufficiently, the moisture content ofthe entirety of the developer is preferably less than 10% by mass, andthe developer more preferably substantially does not contain moisture.

The concentration of the organic solvent (a sum total content in a casewhere a plurality of solvents are mixed together) in the developer ispreferably 50% by mass or more, more preferably 85% % by mass or more,still preferably 90% by mass or more, and particularly preferably 95% bymass or more, and a case where the developer is formed of substantiallyonly an organic solvent is the most preferable. Moreover, a case wherethe developer is formed of substantially only an organic solventincludes a case where components such as trace amounts of a surfactant,an antioxidant, a stabilizer, and an anti-foaming agent are contained ina case where the developer is contained in the amount of 100% by mass.

Moreover, suitable examples of the organic solvent used in the developeralso include, in addition to the above-mentioned ester-based solvents,an ester-based solvent represented by General Formula (S1) or GeneralFormula (S2), which will be described later. As the ester-based solvent,the solvent represented by General Formula (S1) is preferably used amongthe ester-based solvents represented by General Formula (S1) or GeneralFormula (S2), alkyl acetate is still more preferable, and butyl acetate,amyl acetate (pentyl acetate), or isoamyl acetate (isopentyl acetate) isstill more preferable.R—C(═O)—O—R′  General Formula (S1)

In General Formula (S1), R and R′ each independently represent ahydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, analkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group,or a halogen atom. R and R′ may be bonded to each other to form a ring.

The number of carbon atoms in the alkyl group, the alkoxyl group, andthe alkoxycarbonyl group represented by R and R′ is preferably 1 to 15,and the number of carbon atoms in the cycloalkyl group represented by Rand R′ is preferably 3 to 15.

As R and R′, a hydrogen atom or an alkyl group is preferable. The alkylgroup, the cycloalkyl group, the alkoxyl group, and the alkoxycarbonylgroup for R and R′, and a ring which is formed by R and R′ being bondedto each other may be substituted with a hydroxyl group, a group (forexample, an acyl group, an aldehyde group, or an alkoxycarbonyl group)including a carbonyl group, or a cyano group.

Examples of the solvent represented by General Formula (S1) includemethyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amylacetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate,propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethylcarbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethylpyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethylacetoacetate, methyl propionate, ethyl propionate, propyl propionate,isopropyl propionate, methyl 2-hydroxypropionate, and ethyl2-hydroxypropionate.

Among these, it is preferable that R and R′ are each an unsubstitutedalkyl group.

As the solvent represented by General Formula (S1), alkyl acetate ispreferable, butyl acetate, amyl acetate (pentyl acetate), or isoamylacetate (isopentyl acetate) is more preferable, and isoamyl acetate isstill more preferable.

The solvent represented by General Formula (S1) may be used incombination with one or more other organic solvents. The solvent to becombined is not particularly limited as long as it can be mixed with thesolvent represented by General Formula (S1) without being separatedtherefrom. A combination of the solvents represented by General Formula(S1) may be used, or a mixture of the solvent represented by GeneralFormula (S1) and a solvent selected from the group consisting of otherester-based solvents, ketone-based solvents, alcohol-based solvents,amide-based solvents, ether-based solvents, and hydrocarbon-basedsolvents may be used. As the solvent to be combined, one or more kindsmay be used, but one kind is preferably used from the viewpoint ofobtaining stable performance. In a case where a mixture of the solventrepresented by General Formula (S1) and one solvent to be combined isused, a mixing ratio of the solvent represented by General Formula (S1)to the solvent to be combined is usually 20:80 to 99:1, preferably 50:50to 97:3, more preferably 60:40 to 95:5, and most preferably 60:40 to90:10 in terms of a mass ratio.

As the organic solvent used in the developer, a glycol ether-basedsolvent may be used. As the glycol ether-based solvent, a solventrepresented by General Formula (S2) may be used.R″—C(═O)—O—R′″—O—R″″  General Formula (S2)

In General Formula (S2),

R″ and R″″ each independently represent a hydrogen atom, an alkyl group,a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, acarboxyl group, a hydroxyl group, a cyano group, or a halogen atom. R″and R″″ may be bonded to each other to form a ring.

R″ and R″″ are each preferably a hydrogen atom or an alkyl group. Thenumber of carbon atoms in the alkyl group, the alkoxyl group, and thealkoxycarbonyl group for R″ and R″″ is preferably in the range of 1 to15, and the number of carbon atoms in the cycloalkyl group representedby R″ and R″″ is preferably 3 to 15.

R′″ represents an alkylene group or a cycloalkylene group. R′″ ispreferably an alkylene group. The number of carbon atoms in the alkylenegroup for R′″ is preferably in the range of 1 to 10, and the number ofcarbon atoms in the cycloalkylene group is preferably in the range of 3to 10.

The alkyl group, the cycloalkyl group, the alkoxyl group, or thealkoxycarbonyl group for R″ and R″″, the alkylene group or thecycloalkylene group for R′″, and a ring which is formed by R″ and R″″being bonded to each other may be substituted with a hydroxyl group, agroup (for example, an acyl group, an aldehyde group, and analkoxycarbonyl group) including a carbonyl group, or a cyano group.

In General Formula (S2), the alkylene group for R′″ may have an etherbond in an alkylene chain.

Examples of the solvent represented by General Formula (S2) includepropylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monopropyl ether acetate, ethylene glycolmonobutyl ether acetate, ethylene glycol monophenyl ether acetate,diethylene glycol monomethyl ether acetate, diethylene glycol monopropylether acetate, diethylene glycol monophenyl ether acetate, diethyleneglycol monobutyl ether acetate, diethylene glycol monoethyl etheracetate, propylene glycol monoethyl ether acetate, propylene glycolpropyl ether acetate, methyl-3-methoxypropionate,ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate,propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate,2-methoxy butyl acetate, 3-methoxy butyl acetate, 4-methoxy butylacetate, 3-methyl-3-methoxy butyl acetate, 3-ethyl-3-methoxy butylacetate, 2-ethoxy butyl acetate, 4-ethoxy butyl acetate, 4-propoxy butylacetate, 2-methoxy pentyl acetate, 3-methoxy pentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxy pentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxy pentyl acetate, and4-methyl-4-methoxy pentyl acetate, with propylene glycol monomethylether acetate being preferable.

Among these, it is preferable that R″ and R″″ are each an unsubstitutedalkyl group, and R′″ is an unsubstituted alkylene group, it is morepreferable that R″ and R″″ are each a methyl group or an ethyl group,and it is still more preferable that R″ and R″″ are each a methyl group.

The solvent represented by General Formula (S2) may be used incombination with one or more other organic solvents. The solvent to becombined is not particularly limited as long as it can be mixed with thesolvent represented by General Formula (S2) without being separatedtherefrom. A combination of the solvents represented by General Formula(S2) may be used, or a mixture of the solvent represented by GeneralFormula (S2) and a solvent selected from the group consisting of otherester-based solvents, ketone-based solvents, alcohol-based solvents,amide-based solvents, ether-based solvents, and hydrocarbon-basedsolvents may be used. As the solvent to be combined, one or more kindsmay be used, but one kind is preferably used from the viewpoint ofobtaining stable performance. In a case where a mixture of the solventrepresented by General Formula (S2) and one solvent to be combined isused, the mixing ratio of the solvent represented by General Formula(S2) to the solvent to be combined is usually 20:80 to 99:1, preferably50:50 to 97:3, more preferably 60:40 to 95:5, and most preferably 60:40to 90:10 by mass in terms of a mass ratio.

In addition, suitable examples of the organic solvent used in thedeveloper also include, in addition to the above-mentioned ether-basedsolvents, an ether-based solvent having one or more aromatic rings.Among those, a solvent represented by General Formula (S3) ispreferable, and anisole is more preferable.

In General Formula (S3),

R_(S) represents an alkyl group. As the alkyl group, an alkyl grouphaving 1 to 4 carbon atoms is preferable, a methyl group or an ethylgroup is more preferable, and a methyl group is still more preferable.

As the organic solvent included in the developer, an organic solventused in an actinic ray-sensitive or radiation-sensitive resincomposition which will be described later can be used.

<Rinsing Liquid which can be Used in Combination with Treatment Liquidof Present Invention, or Organic Solvent Used in Rinsing Liquid>

The vapor pressure of the organic solvent used in the rinsing liquid (inthe case of a mixed solvent, the total vapor pressure) is preferablyfrom 0.05 kPa to 5 kPa, more preferably from 0.1 kPa to 5 kPa, and stillmore preferably from 0.12 kPa to 3 kPa, at 20° C. By adjusting the vaporpressure of the rinsing liquid to from 0.05 kPa to 5 kPa, thetemperature uniformity in the wafer surface is improved, the swellingcaused by the penetration of the rinsing liquid is also suppressed, andthus, the dimensional uniformity within a wafer surface is improved.

As the organic solvent included in the rinsing liquid, various organicsolvents are used, but at least one organic solvent selected from thegroup consisting of a hydrocarbon-based solvent, a ketone-based solvent,an ester-based solvent, an alcohol-based solvent, an amide-basedsolvent, and an ether-based solvent is preferably used.

Specific examples of these organic solvents are the same as those of theorganic solvent described above for the developer.

In a case where extreme ultraviolet (EUV) light or electron beams (EB)are used in an exposing step which will be described later, as theorganic solvent included in the rinsing liquid, a hydrocarbon-basedsolvent is preferably used, and an aliphatic hydrocarbon-based solventis more preferably used, among the above-mentioned organic solvents. Asthe aliphatic hydrocarbon-based solvent used in the rinsing liquid, fromthe viewpoint of further improving the effects, an aliphatichydrocarbon-based solvent having 5 or more carbon atoms (for example,pentane, hexane, octane, decane, undecane, dodecane, and hexadecane) ispreferable, an aliphatic hydrocarbon-based solvent having 8 or morecarbon atoms is more preferable, and an aliphatic hydrocarbon-basedsolvent having 10 or more carbon atoms is still more preferable.

Incidentally, the upper limit value of the number of carbon atoms in thealiphatic hydrocarbon-based solvent is not particularly limited and, forexample, is 16 or less, preferably 14 or less, and more preferably 12 orless.

Among the aliphatic hydrocarbon-based solvents, decane, undecane, ordodecane is particularly preferable, and undecane is the mostpreferable.

In addition, as the hydrocarbon-based solvent included in the rinsingliquid, an unsaturated hydrocarbon-based solvent can be used, andexamples thereof include unsaturated hydrocarbon-based solvents such asoctene, nonene, decene, undecene, dodecene, and hexadecene. The numberof double bonds and triple bonds in the unsaturated hydrocarbon solventis not particularly limited, and a hydrocarbon chain may be present atan arbitrary position. In addition, in a case where the unsaturatedhydrocarbon solvent has a double bond, cis isomers and trans isomers maycoexist.

By using the hydrocarbon-based solvent (in particular, the aliphatichydrocarbon-based solvent) as the organic solvent included in therinsing liquid, a small amount of the developer permeating into thedeveloped resist film is rinsed, the swelling is further suppressed, andthus, an effect of suppressing pattern collapse is further exhibited.

In addition, as the organic solvent included in the rinsing liquid, amixed solvent of the ester-based solvent and the hydrocarbon-basedsolvent or a mixed solvent of the ketone-based solvent and thehydrocarbon solvent may be used. It is preferable that the mixed solventincludes a hydrocarbon solvent as a major component.

Furthermore, from the viewpoint that the ester-based solvent and theketone-based solvent are particularly effective for reducing a residueafter development, at least one selected from the group consisting ofthe ester-based solvent and the ketone-based solvent may be used as theorganic solvent included in the rinsing liquid in an embodiment.

In a case where the rinsing liquid contains at least one selected fromthe group consisting of the ester-based solvent and the ketone-basedsolvent, it is preferable that the rinsing liquid contains at least onesolvent selected from the group consisting of butyl acetate, isopentylacetate (isoamyl acetate), n-pentyl acetate, ethyl 3-ethoxypropionate(EEP), and 2-heptanone as a major component, and it is more preferablethat the rinsing liquid contains at least one solvent selected from thegroup consisting of butyl acetate and 2-heptanone as a major component.

In addition, in a case where the rinsing liquid contains at least oneselected from the group consisting of the ester-based solvent and theketone-based solvent, it is preferable that the rinsing liquid containsa solvent selected from the group consisting of an ester-based solvent,a glycol ether-based solvent, a ketone-based solvent, and analcohol-based solvent as a minor component, and it is more preferablethat the rinsing liquid contains a solvent selected from the groupconsisting of propylene glycol monomethyl ether acetate (PGMEA),propylene glycol monomethyl ether (PGME), ethyl acetate, ethyl lactate,3-methyl methoxypropionate, cyclohexanone, methyl ethyl ketone,γ-butyrolactone, propanol, 3-methoxy-1-butanol, N-methylpyrrolidone, andpropylene carbonate.

In particular, in a case where an ester-based solvent is used as theorganic solvent, it is preferable that two or more ester-based solventsare used in a view that the effects are further exhibited. Specificexamples of the case include a case where an ester-based solvent(preferably butyl acetate) is used as a major component and anotherester-based solvent having a different chemical structure (preferablypropylene glycol monomethyl ether acetate (PGMEA)) is used as a minorcomponent.

In addition, in a case where an ester-based solvent is used as theorganic solvent, a glycol ether-based solvent may be used, in additionto an ester-based solvent (one kind or two or more kinds), from theviewpoint of further exhibiting the effects. Specific examples of thecase include a case where an ester-based solvent (preferably butylacetate) is used as a major component and a glycol ether-based solvent(preferably propylene glycol monomethyl ether (PGME)) is used as a minorcomponent.

In a case where a ketone-based solvent is used as the organic solvent,an ester-based solvent and/or a glycol ether-based solvent may also beused, in addition to the (one kind or two or more kinds of) ketone-basedsolvent, in a view that the effects are further exhibited. Specificexamples of the case include a case where a ketone-based solvent(preferably 2-heptanone) is used as a major component and an ester-basedsolvent (preferably, propylene glycol monomethyl ether acetate (PGMEA))and/or a glycol ether-based solvent (preferably propylene glycolmonomethyl ether (PGME)) is used as a minor component.

Here, the above-mentioned “major component” indicates that the contentof the component is 50% to 100% by mass, preferably 70% to 100% by mass,more preferably 80% to 100% by mass, still more preferably 90% to 100%by mass, and particularly preferably 95% to 100% by mass, with respectto the total mass of the organic solvent.

In addition, in a case where the minor component is contained, thecontent of the minor component is preferably 0.1% to 20% by mass, morepreferably 0.5% to 10% by mass, and still more preferably 1% to 5% bymass, with respect to the total mass (100% by mass) of the majorcomponent.

A plurality of the organic solvents may be mixed, or the solvent may beused in combination with an organic solvent other than theabove-mentioned solvents. The solvent may also be mixed with water, butthe moisture content in the rinsing liquid is usually 60% by mass orless, preferably 30% by mass or less, more preferably 10% by mass orless, and most preferably 5% by mass or less. By adjusting the moisturecontent to 60% by mass or less, excellent rinsing characteristics can beobtained.

Hereinafter, various additives which can be included in the treatmentliquid of the present invention will be described in detail. Variousadditives shown below may certainly be included in the above-mentioneddeveloper and/or rinsing liquid which can be used in combination withthe treatment liquid of the present invention.

<Surfactant>

It is preferable that the treatment liquid contains a surfactant, whichimproves the wettability for a resist film and allows the developmentand/or the rinsing to proceed more effectively.

As the surfactant, the same one as the surfactant used in an actinicray-sensitive or radiation-sensitive resin composition which will bedescribed later can be used.

The content of the surfactant is usually 0.001% to 5% by mass,preferably 0.005% to 2% by mass, and still more preferably 0.01% to 0.5%by mass, with respect to the total mass of the treatment liquid.

<Antioxidant>

It is preferable that the treatment liquid contains an antioxidant,which can suppress the generation of an oxidant over time and furtherreduce the content of the oxidant.

Known antioxidants may be used as the antioxidant, but in a case wherethe antioxidant is used for semiconductor applications, an amine-basedantioxidant or a phenol-based antioxidant is preferably used.

Examples of the amine-based antioxidant include a naphthylamine-basedantioxidant such as 1-naphthylamine, phenyl-1-naphthylamine,p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine,p-dodecylphenyl-1-naphthylamine, and phenyl-2-naphthylamine; aphenylenediamine-based antioxidant such asN,N′-diisopropyl-p-phenylenediamine, N,N′-diisobutyl-p-phenylenediamine,N,N′-diphenyl-p-phenylenediamine, N,N′-di-β-naphthyl-p-phenylenediamine,N-phenyl-N′-isopropyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine,dioctyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine, andphenyloctyl-p-phenylenediamine; a diphenylamine-based antioxidant suchas dipyridylamine, diphenylamine, p,p′-di-n-butyldiphenylamine,p,p′-di-t-butyldiphenylamine, p,p′-di-t-pentyldiphenylamine,p,p′-dioctyldiphenylamine, p,p′-dinonyldiphenylamine,p,p′-didecyldiphenylamine, p,p′-didodecyldiphenylamine,p,p′-distyryldiphenylamine, p,p′-dimethoxydiphenylamine,4,4′-bis(4-α,α-dimethylbenzoyl)diphenylamine, p-isopropoxydiphenylamine,and dipyridyl amine; and a phenothiazine-based antioxidant such asphenothiazine, N-methylphenothiazine, N-ethylphenothiazine,3,7-dioctylphenothiazine, phenothiazine carboxylic acid ester, andphenoselenazine.

Examples of the phenol-based antioxidant include2,6-ditertiarybutylphenol (tertiary butyl is hereinafter simply referredto as t-butyl), 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-methylphenol,2,6-di-t-butyl-4-ethylphenol, 2,4-dimethyl-6-t-butylphenol,4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-bis(2,6-di-t-butylphenol),4,4′-bis(2-methyl-6-t-butylphenol),2,2′-methylenebis(4-methyl-6-t-butylphenol),2,2′-methylenebis(4-ethyl-6-t-butylphenol),4,4′-butylidenebis(3-methyl-6-t-butylphenol),4,4′-isopropylidenebis(2,6-di-t-butylphenol),2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(4-methyl-6-nonylphenol),2,2′-isobutylidenebis(4,6-dimethylphenol),2,6-bis(2′-hydroxy-3′-t-butyl-5′-methylbenzyl)-4-methylphenol,3-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, octyl3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, stearyl3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, oleyl3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, dodecyl3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, decyl3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, tetrakis{3-(4-hydroxy-3,5-di-t-butylphenyl)propionyloxymethyl}methane,3-(4-hydroxy-3,5-di-t-butylphenyl)propionic acid glycerin monoester, anester of 3-(4-hydroxy-3,5-di-t-butylphenyl)propionic acid and glycerinmonooleyl ether, 3-(4-hydroxy-3,5-di-t-butylphenyl)propionic acidbutylene glycol diester, 3-(4-hydroxy-3,5-di-t-butylphenyl)propionicacid thiodiglycol diester, 4,4′-thiobis(3-methyl-6-t-butylphenol),4,4′-thiobis(2-methyl-6-t-butylphenol),2,2′-thiobis(4-methyl-6-t-butylphenol),2,6-di-t-butyl-α-dimethylamino-p-cresol,2,6-di-t-butyl-4-(N,N′-dimethylaminomethylphenol),bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide, tris{(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl}isocyanurate,tris(3,5-di-t-butyl-4-hydroxyphenyl)isocyanurate,1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, bis{2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl}sulfide,1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,tetraphthaloyl-di(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl sulfide),6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bis(octylthio)-1,3,5-triazine,2,2-thio-{diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenyl)}propionate,N,N′-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamate),3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane,1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, andbis {3,3′-bis-(4′-hydroxy-3′-t-butylphenyl)butyric acid}glycol ester.

The content of the antioxidant is not particularly limited, but ispreferably 0.0001% to 1% by mass, more preferably 0.0001% to 0.1% bymass, and still more preferably 0.0001% to 0.01% by mass, with respectto the total mass of the treatment liquid. In a case where the contentof the antioxidant is 0.0001% by mass or more, a superior antioxidanteffect is obtained. In a case where the content of the antioxidant is 1%by mass or less, there is a tendency that generation of the residuesafter development and/or rinsing can be suppressed.

<Basic Compound>

It is preferable that the treatment liquid of the present inventioncontains a basic compound. Specific examples of the basic compoundinclude the compounds exemplified as a basic compound (E) which can beincluded in an actinic ray-sensitive or radiation-sensitive resincomposition which will be described later.

Among the basic compounds which can be included in the treatment liquidof the present invention, the following nitrogen-containing compound canbe preferably used.

(Nitrogen-Containing Compound)

In the case where the nitrogen-containing compound is included in thedeveloper, the nitrogen-containing compound can interact with a polargroup generated in a resist film by the action of an acid to furtherimprove the insolubility of the exposed area in an organic solvent.Here, the interaction between the nitrogen-containing compound and thepolar group refers to an action in which the nitrogen-containingcompound and the polar group react to form a salt, an ionic bond, or thelike.

The nitrogen-containing compound is preferably a compound represented byFormula (1).

In Formula (1), R¹ and R² are each independently a hydrogen atom, ahydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonylgroup, a chained hydrocarbon group having 1 to 30 carbon atoms, analicyclic hydrocarbon group having 3 to 30 carbon atoms, an aromatichydrocarbon group having 6 to 14 carbon atoms, or a group formed by acombination of two or more of these groups. R³ is a hydrogen atom, ahydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonylgroup, an n-valent chained hydrocarbon group having 1 to 30 carbonatoms, an n-valent alicyclic hydrocarbon group having 3 to 30 carbonatoms, an n-valent aromatic hydrocarbon group having 6 to 14 carbonatoms, or an n-valent group formed by a combination of two or more ofthese groups. n is an integer of 1 or more. However, in a case where nis 2 or more, a plurality of R¹'s and R²'s may be respectively the sameor different from one another. In addition, any two of R¹ to R³, takentogether with the nitrogen atom to which each is bonded, may form a ringstructure.

Examples of the chained hydrocarbon group having 1 to 30 carbon atoms,represented by R¹ and R², include a methyl group, an ethyl group, ann-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropylgroup, a 1-methylpropyl group, and a t-butyl group.

Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms,represented by R¹ and R², include a cyclopropyl group, a cyclopentylgroup, a cyclohexyl group, an adamantyl group, and a norbornyl group.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms,represented by R¹ and R², include a phenyl group, a tolyl group, and anaphthyl group.

Examples of the group formed by a combination of two or more of thosegroups represented by IV and R² include aralkyl groups having 6 to 12carbon atoms, such as a benzyl group, a phenethyl group, anaphthylmethyl group, and a naphthylethyl group.

Examples of the n-valent chained hydrocarbon group having 1 to 30 carbonatoms, represented by R³, include groups formed by removing (n−1)hydrogen atoms from the same groups as those groups exemplified as thechained hydrocarbon group having 1 to 30 carbon atoms, represented by R¹and R².

Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms,represented by R³, include groups formed by removing (n−1) hydrogenatoms from the same groups as those groups exemplified as the cyclichydrocarbon group having 3 to 30 carbon atoms, represented by R¹ and R².

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms,represented by R³, include groups formed by removing (n−1) hydrogenatoms from the same groups as those groups exemplified as the aromatichydrocarbon group having 6 to 14 carbon atoms, represented by R¹ and R².

Examples of the group formed by a combination of two or more of thosegroups represented by R³ include groups formed by removing (n−1)hydrogen atoms from the same groups as those groups exemplified as thegroup formed by a combination of two or more of those groups representedby R¹ and R².

The groups represented by R¹ to R³ may be substituted. Specific examplesof the substituent include a methyl group, an ethyl group, a propylgroup, an n-butyl group, a t-butyl group, a hydroxyl group, a carboxygroup, a halogen atom, and an alkoxy group. Examples of the halogen atominclude a fluorine atom, a chlorine atom, and a bromine atom. Examplesof the alkoxy group include a methoxy group, an ethoxy group, a propoxygroup, and a butoxy group.

Examples of the compound represented by Formula (1) include a(cyclo)alkylamine compound, a nitrogen-containing heterocyclic compound,an amide group-containing compound, and a urea compound.

Examples of the (cyclo)alkylamine compound include a compound having onenitrogen atom, a compound having two nitrogen atoms, and a compoundhaving three or more nitrogen atoms.

Examples of the (cyclo)alkylamine compound having one nitrogen atominclude mono(cyclo)alkylamines such as n-hexylamine, n-heptylamine,n-octylamine, n-nonylamine, 1-aminodecane, and cyclohexylamine;di(cyclo)alkylamines such as di-n-butylamine, di-n-pentylamine,di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine,di-n-decylamine, cyclohexylmethylamine, and dicyclohexylamine;tri(cyclo)alkylamines such as triethylamine, tri-n-propylamine,tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine,tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine,cyclohexyldimethylamine, methyldicyclohexylamine, andtricyclohexylamine; substituted alkylamines such as triethanolamine; andaromatic amines such as aniline, N-methylaniline, N,N-dimethylaniline,2-methylaniline, 3-methylaniline, 4-methylaniline, N,N-dibutylaniline,4-nitroaniline, diphenylamine, triphenylamine, naphthylamine,2,4,6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine,2,6-diisopropylaniline, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane,and 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane.

Examples of the (cyclo)alkylamine compound having two nitrogen atomsinclude ethylenediamine, tetramethylethylenediamine,tetramethylenediamine, hexamethylenediamine,4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylether,4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine,2,2-bis(4-aminophenyl)propane,2-(3-aminophenyl)-2-(4-aminophenyl)propane,1,4-bis[1-(4-aminophenyl)-1-methylethyl]benzene,1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene,bis(2-dimethylaminoethyl)ether, bis(2-diethylaminoethyl)ether,1-(2-hydroxyethyl)-2-imidazolidinone, 2-quinoxalinol, andN,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenedi amine.

Examples of the (cyclo)alkylamine compound having three or more nitrogenatoms include polymers such as polyethyleneimine, polyallylamine, and2-dimethylaminoethylacrylamide.

Examples of the nitrogen-containing heterocyclic compound include anitrogen-containing aromatic heterocyclic compound and anitrogen-containing aliphatic heterocyclic compound.

Examples of the nitrogen-containing aromatic heterocyclic compoundinclude imidazoles such as imidazole, 4-methylimidazole,4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole,1-benzyl-2-methylimidazole, and 1-benzyl-2-methyl-1H-imidazole; andpyridines such as pyridine, 2-methylpyridine, 4-methylpyridine,2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine,2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acidamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, and2,2′:6′,2″-terpyridine.

Examples of the nitrogen-containing aliphatic heterocyclic compoundinclude piperazines such as piperazine and 1-(2-hydroxyethyl)piperazine;pyrazine, pyrazole, pyridazine, quinoxaline, purine, pyrrolidine,proline, piperidine, piperidineethanol, 3-piperidino-1,2-propanediol,morpholine, 4-methylmorpholine, 1-(4-morpholinyl)ethanol,4-acetylmorpholine, 3-(N-morpholino)-1,2-propanediol,1,4-dimethylpiperazine, and 1,4-diazabicyclo[2.2.2]octane.

Examples of the amide group-containing compound includeN-t-butoxycarbonyl group-containing amino compounds such asN-t-butoxycarbonyldi-n-octylamine, N-t-butoxycarbonyldi-n-nonylamine,N-t-butoxycarbonyldi-n-decylamine, N-t-butoxycarbonyldicyclohexylamine,N-t-butoxycarbonyl-1-adamantylamine, N-t-butoxycarbonyl-2-adamantylamine, N-t-butoxycarbonyl-N-methyl-1-adamantylamine,(S)-(−)-1-(t-butoxycarbonyl)-2-pyrrolidinemethanol,(R)-(+)-1-(t-butoxycarbonyl)-2-pyrrolidinemethanol,N-t-butoxycarbonyl-4-hydroxypiperidine, N-t-butoxycarbonylpyrrolidine,N-t-butoxycarbonylpiperazine, N,N-di-t-butoxycarbonyl-1-adamantylamine,N,N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine,N-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, N,N′-di-t-butoxycarbonylhexamethylenediamine, N,N,N′,N′-tetra-t-butoxycarbonylhexamethylenediamine, N,N′-di-t-butoxycarbonyl-1,7-diaminoheptane,N,N′-di-t-butoxycarbonyl-1,8-diaminooctane,N,N′-di-t-butoxycarbonyl-1,9-diaminononane, N,Nt-di-t-butoxycarbonyl-1,10-diaminodecane,N,N′-di-t-butoxycarbonyl-1,12-diaminododecane,N,N′-di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane,N-t-butoxycarbonylbenzimidazole,N-t-butoxycarbonyl-2-methylbenzimidazole, andN-t-butoxycarbonyl-2-phenylbenzimidazole; formamide, N-methylformamide,N,N-dimethylformamide, acetamide, N-methylacetamide,N,N-dimethylacetamide, propionamide, benzamide, pyrrolidone,N-methylpyrrolidone, N-acetyl-1-adamantylamine, and tris(2-hydroxyethyl)isocyanurate.

Examples of the urea compound include urea, methylurea,1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea,1,3-diphenylurea, and tri-n-butylthiourea.

Among the above-mentioned nitrogen-containing compounds, anitrogen-containing compound having an SP value of 18 or less ispreferably used from the viewpoint of suppressing development defects.This is because the nitrogen-containing compound having an SP value of18 or less has a good affinity with a rinsing liquid used in a rinsingprocess which will be described later, and is thus capable ofsuppressing the occurrence of development defects such as precipitation.

The SP value of the nitrogen-containing compound used in the presentinvention is calculated using the Fedors method described in “Propertiesof Polymers, 2^(nd) edition, 1976”. The calculation formula used and theparameters of each substituent are shown below.SP value(Fedors method)=[(Sum of cohesive energies of individualsubstituents)/(Sum of volumes of individual substituents)]^(0.5)

TABLE 1 Cohesive energy Volume Substituent (J/mol) (cm³/mol) CH₃ 4,71033.5 CH₂ 4,940 16.1 CH 3,430 −1 C 1,470 −19.2 CH₂= 4,310 28.5 ═CH— 4,31013.5 ═C< 4,310 −5.5 Ph 31,940 71.4 NH₂ 12,560 19.2 NH 8,370 4.5 N< 4,190−9 CN 25,530 24 OH 29,800 10 CHO 21,350 22.3 COOH 27,630 28.5 —O— 3,3503.8 CO 17,370 10.8 COO 18,000 18 5-Membered or 1,050 16 higher ringFedors substituent constants extracted (Properties of Polymers, 2^(nd)edition, pp. 138 to 140)

Among those, preferred is a (cyclo)alkylamine compound or anitrogen-containing aliphatic heterocyclic compound, which satisfies theabove-mentioned conditions (SP value), and more preferred is1-aminodecane, di-n-octylamine, tri-n-octylamine, ortetramethylethylenediamine. The SP values and the like of thesenitrogen-containing aliphatic heterocyclic compounds are shown in thefollowing table.

TABLE 2 CH₃ CH₂ NH₂ NH N SP value 1-Aminodecane 1 9 1 17.7Di-n-octylamine 2 14 1 17.1 Tri-n-octylamine 3 21 1 16.9Tetramethylethylenediamine 4 2 2 15.8

The content of the basic compound (preferably the nitrogen-containingcompound) in the treatment liquid is not particularly limited, but ispreferably 10% by mass or less, and more preferably 0.5% to 5% by mass,with respect to the total amount of the treatment liquid, from theviewpoint that the effect of the present invention is superior.

In addition, in the present invention, the above-mentionednitrogen-containing compounds may be used singly or two or more of thecompounds having different chemical structures may be used incombination.

The above-mentioned treatment liquid can also be suitably applied to anon-chemically amplified resist for the purpose of, for example, solvingthe problems of the present application.

Examples of the non-chemically amplified resist include the followingones.

(1) A resist material in which a main chain is cut, the molecular weightdecreases, and the solubility changes upon irradiation with a g-ray, ah-ray, an i-ray, KrF, ArF, EB, EUV, or the like (for example, a resistmaterial including a copolymer of an α-chloroacrylate compound and anα-methylstyrene compound as a major component, which is described inparagraphs 0025 to 0029, and 0056 of JP2013-210411A and 0032 to 0036,and 0063 of US2015/0008211A).

(2) A resist material such as a hydrogen silsesquioxane resist (HSQ) anda chlorine-substituted calixarene in which a silanol condensationreaction occurs with a g-ray, a h-ray, an i-ray, KrF, ArF, EB, EUV, orthe like.

(3) A resist which includes a metal complex (a complex of magnesium,chromium, manganese, iron, cobalt, nickel, copper, zinc, silver,cadmium, indium, tin, antimony, cesium, zirconium, hafnium, or the like;titanium, zirconium, or hafnium is preferable from the viewpoint ofpattern formability) having an absorption to light such as a g-ray, ah-ray, an i-ray, KrF, ArF, EB, and EUV, and in which liganddisengagement or ligand exchange occurs in a case of being used incombination with a photoacid generator (for example, a resist materialdescribed in 0017 to 0033, and 0037 to 0047 of JP2015-075500A, inparagraphs 0017 to 0032, and 0043 to 0044 of JP2012-185485A, paragraphs0042 to 0051, and 0066 of US2012/0208125A, and the like)

In addition, the above-mentioned treatment liquid can also be suitablyapplied to a silicon-based resist for the purpose of, for example,solving the problems of the present application.

Examples of the silicon-based resist include the resist materialsdescribed in paragraphs 0010 to 0062 and paragraphs 0129 to 0165 ofJP2008-83384A.

[Pattern Forming Method]

The pattern forming method of the present invention includes a resistfilm forming step of forming a resist film using an actinicray-sensitive or radiation-sensitive resin composition (hereinafter alsoreferred to as a “resist composition”), an exposing step of exposing theresist film, and a treating step of treating the exposed resist filmwith the above-described treatment liquid.

According to the pattern forming method of the present invention, theabove-mentioned treatment liquid is used, and therefore, it is possibleto simultaneously suppress the occurrence of pattern collapse in aresist L/S pattern and the occurrence of omission failure in a resistC/H pattern.

Hereinafter, the respective steps of the pattern forming method of thepresent invention will be described. In addition, as an example of thetreating step, each of a developing step and a rinsing step will bedescribed.

<Resist Film Forming Step>

The resist film forming step is a step of forming a resist film using anactinic ray-sensitive or radiation-sensitive resin composition and, forexample, can be carried out using the following method.

In order to form the resist film (actinic ray-sensitive orradiation-sensitive resin composition film) on the substrate using theactinic ray-sensitive or radiation-sensitive resin composition,respective components described below are dissolved in a solvent toprepare an actinic ray-sensitive or radiation-sensitive resincomposition, the actinic ray-sensitive or radiation-sensitive resincomposition is optionally filtered through a filter and applied to thesubstrate. As the filter, a polytetrafluoroethylene-, polyethylene- ornylon-made filter having a pore size of preferably 0.1 microns or less,more preferably 0.05 microns or less, and still more preferably 0.03microns or less is preferable.

The actinic ray-sensitive or radiation-sensitive resin composition isapplied to the substrate (e.g.: a silicon dioxide-coated substrate),which is used for manufacturing an integrated circuit element, using anappropriate coating method such as a method using a spinner. Next, theactinic ray-sensitive or radiation-sensitive resin composition is driedto form a resist film. Optionally, various undercoating films (aninorganic film, an organic film, or an antireflection film) may beformed below the resist film.

As the drying method, a method of drying heating the composition isgenerally used. Heating may be carried out using means provided in atypical exposure or developing device, and may be carried out using ahot plate or the like.

The heating temperature is preferably 80° C. to 180° C., more preferably80° C. to 150° C., still more preferably 80° C. to 140° C., andparticularly preferably 80° C. to 130° C.

The heating time is preferably 30 to 1,000 seconds, more preferably 60to 800 seconds, and still more preferably 60 to 600 seconds.

The film thickness of the resist film is generally 200 nm or less, andpreferably 100 nm or less.

For example, in order to resolve a 1:1 line-and-space pattern having asize of 30 nm or less, the film thickness of a resist film to be formedis preferably 50 nm or less. In a case where a resist film having a filmthickness of 50 nm or less is applied to a developing step describedbelow, pattern collapse is not likely to occur, and higher resolutionperformance can be obtained.

The film thickness is more preferably in a range of 15 nm to 45 nm. In acase where the film thickness is 15 nm or more, sufficient etchingresistance is obtained. The film thickness is still more preferably isin a range of 15 nm to 40 nm. In a case where the film thickness is inthe range, etching resistance and higher resolution performance can besimultaneously satisfied.

Moreover, in the pattern forming method of the present invention, anupper layer film (topcoat film) may be formed on the upper layer of theresist film. The upper layer film can be formed by using, for example, acomposition for forming an upper layer film, which contains ahydrophobic resin, an acid generator, and a basic compound. The upperlayer film and the composition for forming an upper layer film are thesame as described later.

<Exposing Step>

The exposing step is a step of exposing the resist film and can becarried out by using the following method, for example.

The resist film formed as described above is irradiated with actinicrays or radiation through a predetermined mask. For irradiation of anelectron beam, drawing (direct drawing) not using a mask is generallyused. Further, a pre-exposure baking step ((also referred to aspost-application baking (PB; prebaking)) is preferably included afterthe formation of the film and before the exposing step.

The actinic rays or radiation is not particularly limited, and is, forexample, KrF excimer laser, ArF excimer laser, extreme ultraviolet (EUV)light, electron beams (EB), or the like. The exposure may be liquidimmersion exposure.

<Baking>

In the pattern forming method of the present invention, it is preferablethat a post-exposure baking (PEB) after the exposing step and before thedeveloping step. Due to the post-exposure baking step, a reaction of anexposed area is promoted, and the sensitivity or the pattern profile isimproved.

The heating temperature is preferably 80° C. to 150° C., more preferably80° C. to 140° C., and still more preferably 80° C. to 130° C.

The heating time is preferably 30 to 1,000 seconds, more preferably 60to 800 seconds, and still more preferably 60 to 600 seconds.

Heating may be carried out using means provided in a typical exposure ordeveloping device, and may be carried out using a hot plate or the like.

In addition, the heating temperature and the heating time of theabove-mentioned pre-exposure baking step are the same as the heatingtemperature and the heating time of the above-mentioned post-exposurebaking step.

<Developing Step>

The developing step is a step of developing the exposed resist film witha developer.

As a developing method, for example, a method in which a substrate isdipped in a tank filled with a developer for a certain period of time (adip method), a method in which a developer is heaped up to the surfaceof a substrate by surface tension and developed by maintaining for acertain period of time (a puddle method), a method in which a developeris sprayed on the surface of a substrate (a spray method), or a methodin which a developer is continuously discharged on a substrate rotatedat a constant rate while scanning a developer discharging nozzle at aconstant rate (a dynamic dispense method) can be applied.

In addition, a step of stopping development while replacing the solventwith another solvent may be carried out after the developing step.

The developing time is not particularly limited as long as it is aperiod of time where a non-exposed area of a resin is sufficientlydissolved. The development time is usually 10 to 300 seconds andpreferably 20 to 120 seconds.

The temperature of the developer is preferably 0° C. to 50° C., and morepreferably 15° C. to 35° C.

As the developer used in the developing step, the above-describedtreatment liquid is preferably used. The developer is as describedabove. In addition to the development using the treatment liquid,development using an alkali developer may further be carried out(so-called double development).

<Rinsing Step>

The rinsing step is a step of carrying out washing (rinsing) with arinsing liquid after the developing step.

In the rinsing step, the developed wafer is subjected to a washingtreatment using the above-described rinsing liquid.

A rinsing method is not particularly limited, and for example, a methodin which a rinsing liquid is continuously discharged to a substratewhich is rotating at a constant rate (a rotation discharging method), amethod in which a substrate is dipped in a tank filled with a rinsingliquid for a certain period of time (a dip method), or a method in whicha rinsing liquid is sprayed on the surface of a substrate (a spraymethod) can be applied, and among these, it is preferable that a rinsingtreatment is carried out using the rotation discharging method, and therinsed substrate is rotated at a rotation speed of 2,000 rpm to 4,000rpm to remove the rinsing liquid from the substrate.

The rinsing time is not particularly limited, and is usually 10 secondsto 300 seconds, preferably 10 seconds to 180 seconds, and mostpreferably 20 seconds to 120 seconds.

The temperature of the rinsing liquid is preferably 0° C. to 50° C., andmore preferably 15° C. to 35° C.

In addition, after the development treatment or the rinsing treatment, atreatment of removing the developer or the rinsing liquid which isattached to the pattern, using a supercritical fluid, may be carriedout.

Incidentally, after the development treatment, the rinsing treatment, orthe treatment using the supercritical fluid, a heating treatment can becarried out so as to remove the solvent remaining in the pattern. Theheating temperature is not particularly limited as long as a good resistpattern is obtained, and is usually 40° C. to 160° C. The heatingtemperature is preferably 50° C. to 150° C., and most preferably 50° C.to 110° C. The heating time is not particularly limited as long as agood resist pattern is obtained, but is usually 15 to 300 seconds andpreferably 15 to 180 seconds.

In the pattern forming method of the present invention, it is preferablethat at least one of the developer or the rinsing liquid is theabove-described treatment liquid, but it is particularly preferable thatthe rinsing liquid is the above-mentioned treatment liquid.

Moreover, in general, the developer and the rinsing liquid are stored ina waste liquid tank through a pipe after use. At this time, in a casewhere an ester-based solvent is used as the developer and ahydrocarbon-based solvent is used as the rinsing liquid, the resistdissolved in the developer precipitates, is attached to side and backsurfaces of a wafer, a side surface of the pipe, and the like, andcontaminates a device.

In order to solve the problems, a method of passing a solvent fordissolving a resist through the pipe again may be used. Examples of themethod of passing a solvent through a pipe include a method in which aside surface, a back surface, or the like of a substrate which has beenwashed with the rinsing liquid is washed by passing a solvent fordissolving the resist therethrough, and a method in which a solvent fordissolving a resist is passed through a pipe while being not broughtinto contact with the resist.

The solvent which is passed through the pipe is not particularly limitedas long as it can dissolve the resist, and examples thereof include theabove-mentioned organic solvents used as a developer. Specific examplesthereof include propylene glycol monomethyl ether acetate (PGMEA),propylene glycol monoethyl ether acetate, propylene glycol monopropylether acetate, propylene glycol monobutyl ether acetate, propyleneglycol monomethyl ether propionate, propylene glycol monoethyl etherpropionate, ethylene glycol monomethyl ether acetate, ethylene glycolmonoethyl ether acetate, propylene glycol monomethyl ether (PGME),propylene glycol monoethyl ether, propylene glycol monopropyl ether,propylene glycol monobutyl ether, ethylene glycol monomethyl ether,ethylene glycol monoethyl ether, 2-heptanone, lactic acid ethyl,1-propanol, and acetone. Among these, PGMEA, PGME, or cyclohexanone ispreferable.

[Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition (ResistComposition)]

Next, the actinic ray-sensitive or radiation-sensitive resin compositionwhich is preferably used in combination with the treatment liquid of thepresent invention will be described in detail. Hereinafter, thecomponents which can be included in the actinic ray-sensitive orradiation-sensitive resin composition will be first described.

(A) Resin

It is preferable that a “resin (A)” is contained as the actinicray-sensitive or radiation-sensitive resin composition which ispreferably used in combination with the treatment liquid of the presentinvention. The resin (A) has at least (i) a repeating unit having agroup capable of decomposing by the action of an acid to generate acarboxyl group (may further include a repeating unit having a phenolichydroxyl group), or at least (ii) a repeating unit having a phenolichydroxyl group.

Furthermore, in a case where the resin (A) has the repeating unitcapable of decomposing by the action of an acid to generate a carboxylgroup, the solubility in an alkali developer increases and thesolubility in the organic solvent increases due to the action of anacid.

Examples of the repeating unit having a phenolic hydroxyl groupcontained in the resin (A) include a repeating unit represented byGeneral Formula (I).

In the formula,

R₄₁, R₄₂, and R₄₃ each independently represent a hydrogen atom, an alkylgroup, a halogen atom, a cyano group, or an alkoxycarbonyl group. R₄₂may be bonded to Ar₄ to form a ring, and in this case, R₄₂ represents asingle bond or an alkylene group.

X₄ represents a single bond, —COO—, or —CONR₆₄—, and R₆₄ represents ahydrogen atom or an alkyl group.

L₄ represents a single bond or an alkylene group.

Ar₄ represents a (n+1)-valent aromatic ring group, and in a case whereAr₄ is bonded to R₄₂ to form a ring, Ar₄ represents a (n+2)-valentaromatic ring group.

n represents an integer of 1 to 5.

As the alkyl group of R₄₁, R₄₂, and R₄₃ in General Formula (I), an alkylgroup having 20 or less carbon atoms, which may have a substituent, suchas a methyl group, an ethyl group, a propyl group, an isopropyl group, an-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group,an octyl group, and a dodecyl group, is preferable, an alkyl grouphaving 8 or less carbon atoms is more preferable, and an alkyl grouphaving 3 or less carbon atoms is still more preferable.

The alkyl group of R₄₁, R₄₂, and R₄₃ in General Formula (I) may becyclic, and may be monocyclic or polycyclic. In a case where the alkylgroup of R₄₁, R₄₂, and R₄₃ is cyclic, a monocyclic cycloalkyl grouphaving 3 to 8 carbon atoms, which may have a substituent, such as acyclopropyl group, a cyclopentyl group, and a cyclohexyl group, ispreferable.

Examples of the halogen atom of R₄₁, R₄₂, and R₄₃ in General Formula (I)include a fluorine atom, a chlorine atom, a bromine atom, and an iodineatom, with the fluorine atom being preferable.

As the alkyl group included in the alkoxycarbonyl group of R₄₁, R₄₂, andR₄₃ in General Formula (I), the same alkyl groups as described aboveregarding R₄₁, R₄₂, and R₄₃ are preferable.

Preferred examples of a substituent of each of the groups include analkyl group, a cycloalkyl group, an aryl group, an amino group, an amidogroup, an ureido group, a urethane group, a hydroxyl group, a carboxylgroup, a halogen atom, an alkoxy group, a thioether group, an acylgroup, an acyloxy group, an alkoxycarbonyl group, a cyano group, and anitro group, and the number of carbon atoms in the substituent ispreferably 8 or less.

Ar₄ represents an (n+1)-valent aromatic ring group. In a case where n is1, a divalent aromatic ring group may have a substituent, and preferredexamples thereof include an arylene group having 6 to 18 carbon atomssuch as a phenylene group, a tolylene group, a naphthylene group, or ananthracenylene group; and an aromatic ring group having a heterocycle,such as thiophene, furan, pyrrole, benzothiophene, benzofuran,benzopyrrole, triazine, imidazole, benzoimidazole, triazole,thiadiazole, and thiazole. These may further have a substituent.

In a case where n o an integer of 2 or more, specific preferred examplesof the (n+1)-valent aromatic ring group include groups obtained byremoving arbitrary (n−1) hydrogen atoms from the specific examples ofthe above-described divalent aromatic ring groups.

The (n+1)-valent aromatic ring group may further have a substituent.

Examples of a substituent which may be included in the above-mentionedalkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and(n+1)-valent aromatic ring group include the alkyl groups exemplified byR₄₁, R₄₂, and R₄₃ in General Formula (I), alkoxy groups such as amethoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group,a hydroxypropoxy group, and a butoxy group; and aryl group such as aphenyl group.

As an alkyl group of R₆₄ in —CONR₆₄— (R₆₄ represents a hydrogen atom oran alkyl group) represented by X₄, an alkyl group having 20 or lesscarbon atoms, which may have a substituent, such as a methyl group, anethyl group, a propyl group, an isopropyl group, a n-butyl group, asec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, ora dodecyl group is preferable, and an alkyl group having 8 or lesscarbon atoms is more preferable.

As X₄, a single bond, —COO—, or —CONH— is preferable, and a single bondor —COO— is more preferable.

Preferred examples of the alkylene group in L₄ include an alkylene grouphaving 1 to 8 carbon atoms, which may have a substituent, such as amethylene group, an ethylene group, a propylene group, a butylene group,a hexylene group, and an octylene group.

As Ar₄, an aromatic ring group having 6 to 18 carbon atoms, which mayhave a substituent, is more preferable, and a benzene ring group, anaphthalene ring group, or a biphenylene ring group is particularlypreferable.

It is preferable that the repeating unit represented by General Formula(I) includes a hydroxystyrene structure. That is, it is preferable thatAr₄ is a benzene ring group.

Preferred examples of the repeating unit having a phenolic hydroxylgroup contained in the resin (A) include a repeating unit represented byGeneral Formula (p1).

R in General Formula (p1) represents a hydrogen atom or a linear orbranched alkyl group having a halogen atom or 1 to 4 carbon atoms. Aplurality of R's may be the same as or different from each other. As Rin General Formula (p1), a hydrogen atom is preferable.

Ar in General Formula (p1) represents an aromatic ring, and examplesthereof include an aromatic hydrocarbon ring having 6 to 18 carbonatoms, which may have a substituent, such as a benzene ring, anaphthalene ring, an anthracene ring, a fluorene ring, and aphenanthrene ring; and an aromatic heterocycle including a heterocycle,such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophenering, a benzofuran ring, a benzopyrrole ring, a triazine ring, animidazole ring, a benzoimidazole ring, a triazole ring, a thiadiazolering, and a thiazole ring. Among these, a benzene ring is preferable.

m in General Formula (p1) represents an integer of 1 to 5, and ispreferably 1.

Specific examples of the repeating unit having a phenolic hydroxyl groupcontained in the resin (A) are shown below, but the present invention isnot limited thereto. In the formulae, a represents 1 or 2.

The content of the repeating unit having a phenolic hydroxyl group ispreferably 0% to 50% by mole, more preferably 0% to 45% by mole, andstill more preferably 0% to 40% by mole, with respect to all therepeating units of the resin (A).

The repeating unit having a group capable of decomposing by the actionof an acid to generate a carboxyl group contained in the resin (A) is arepeating unit having a group which is substituted with a group obtainedby a hydrogen atom being removed from a carboxyl group due todecomposition caused by the action of an acid.

Examples of the group capable of leaving by an acid include—C(R₃₆)(R₃₇)(R₃₈), —C(R₃₆)(R₃₇)(OR₃₉), and —C(R₀₁)(R₀₂)(OR₃₉).

In the formulae, R₃₆ to R₃₉ each independently represent an alkyl group,a cycloalkyl group, an aryl group, an aralkyl group, or an alkenylgroup. R₃₆ and R₃₇ may be bonded to each other to form a ring.

R₀₁ to R₀₂ each independently represent a hydrogen atom, an alkyl group,a cycloalkyl group, an aryl group, an aralkyl group, or an alkenylgroup.

As the repeating unit having a group capable of decomposing by theaction of an acid to generate a carboxyl group, which is contained inthe resin (A), a repeating unit represented by General Formula (AI) ispreferable.

In General Formula (AI),

Xa₁ represents a hydrogen atom or an alkyl group which may have asubstituent.

T represents a single bond or a divalent linking group.

Rx₁ to Rx₃ each independently represent an (linear or branched) alkylgroup or a (monocyclic or polycyclic) cycloalkyl group. In a case whereall of Rx₁ to Rx₃ represent an alkyl group (linear or branched), it ispreferable that at least two of Rx₁, . . . , or Rx₃ are a methyl group.

Two of Rx₁ to Rx₃ may be bonded to each other to form a (monocyclic orpolycyclic) cycloalkyl group.

Examples of the alkyl group which may have a substituent, represented byXa₁, include a methyl group and a group represented by —CH₂—R₁₁. R₁₁represents a halogen atom (for example, a fluorine atom), a hydroxylgroup, or a monovalent organic group, and examples thereof include analkyl group having 5 or less carbon atoms and an acyl group having 5 orless carbon atoms. In particular, an alkyl group having 3 or less carbonatoms is preferable, and a methyl group is more preferable. In oneaspect, Xa₁ is preferably a hydrogen atom, a methyl group, atrifluoromethyl group, or a hydroxymethyl group.

Examples of the divalent linking group of T include an alkylene group, a—COO-Rt- group, and a —O-Rt- group. In the formulae, Rt represents analkylene group or a cycloalkylene group.

T is preferably a single bond or a —COO-Rt- group. Rt representspreferably an alkylene group having 1 to 5 carbon atoms, and morepreferably a —CH₂— group, a —(CH₂)₂— group, or a —(CH₂)₃— group.

As the alkyl group of Rx₁ to Rx₃, an alkyl group having 1 to 4 carbonatoms such as a methyl group, an ethyl group, a n-propyl group, anisopropyl group, a n-butyl group, an isobutyl group, and a t-butyl groupis preferable.

As the cycloalkyl group of Rx₁ to Rx₃, a monocycloalkyl group such as acyclopentyl group and a cyclohexyl group, or a polycycloalkyl group suchas a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanylgroup, and an adamantyl group is preferable.

As the cycloalkyl group which is formed by two of Rx₁ to Rx₃ beingbonded to each other, a monocycloalkyl group such as a cyclopentyl groupor a cyclohexyl group, and a polycycloalkyl group such as a norbornylgroup, a tetracyclodecanyl group, a tetracyclododecanyl group, and anadamantyl group is preferable. In particular, a monocycloalkyl grouphaving 5 or 6 carbon atoms is preferable.

In the cycloalkyl group which is formed by two of Rx₁ to Rx₃ beingbonded to each other, for example, one methylene group constituting thering may be substituted with a heteroatom such as an oxygen atom, or agroup having a heteroatom, such as a carbonyl group.

In the repeating unit represented by General Formula (AI), for example,it is preferable that Rx₁ is a methyl group or an ethyl group and thatRx₂ and Rx₃ are bonded to each other to form the above-mentionedcycloalkyl group.

Each of the groups may have a substituent, and examples of thesubstituent include an alkyl group (having 1 to 4 carbon atoms), ahalogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbonatoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6carbon atoms), which preferably has 8 or less carbon atoms.

As the repeating unit represented by General Formula (AI), anacid-decomposable tertiary alkyl (meth)acrylate ester-based repeatingunit (a repeating unit in which Xa₁ represents a hydrogen atom or amethyl group, and T represents a single bond) is preferable. A repeatingunit in which Rx₁ to Rx₃ each independently represent a linear orbranched alkyl group is more preferable, and a repeating unit in whichRx₁ to Rx₃ each independently represent a linear alkyl group is stillmore preferable. Further, in the present specification, the(meth)acrylic acid means an acrylic acid and/or a methacrylic acid. Thisshall also apply to a (meth)acryl group and a (meth)acrylate.

Specific examples of the repeating unit having a group capable ofdecomposing by the action of an acid to generate a carboxyl group,contained in the resin (A), are shown below, but the present inventionis not limited thereto.

In the specific examples, Rx and Xa₁ represent a hydrogen atom, CH₃,CF₃, or CH₂OH. Rxa and Rxb each independently represent an alkyl grouphaving 1 to 4 carbon atoms. Z represents a substituent including a polargroup. In a case where Z's are present in plural number, Z's eachindependently represent a substituent having a polar group. p represents0 or a positive integer. Examples of the substituent having a polargroup represented by Z include a linear, branched, or cyclic alkyl grouphaving a hydroxyl group, a cyano group, an amino group, an alkylamidogroup, or a sulfonamide group, an alkyl group having a hydroxyl group ispreferable, and as the branched alkyl group, an isopropyl group isparticularly preferable.

The content of the repeating unit having a group capable of decomposingby the action of an acid to generate a carboxyl group is preferably 15%to 90% by mole, more preferably 20% to 90% by mole, still morepreferably 25% to 80% by mole, and particularly preferably 30% to 70% bymole with respect to all the repeating units of the resin (A).

It is preferable that the resin (A) further contains a repeating unithaving a lactone group.

As the lactone group, any of groups which contain a lactone structuremay be used, but a group having a 5- to 7-membered lactone structurecontaining a lactone structure is preferable, and a group in whichanother ring structure is fused to a group having a 5- to 7-memberedlactone structure so as to form a bicyclo structure or a spiro structureis more preferable.

It is preferable that a repeating unit which contains a group havingwith a lactone structure represented by any one of General Formulae(LC1-1) to (LC1-16) is contained as the repeating group having a lactonegroup. As the lactone structure, a group represented by General Formula(LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), or (LC1-14) is preferable.In addition, the group having a lactone structure may be directly bondedto a main chain.

The lactone structure moiety may or may not have a substituent (Rb₂).Preferred examples of the substituent (Rb₂) include an alkyl grouphaving 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbonatoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonylgroup having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, ahydroxyl group, a cyano group, and an acid-decomposable group. n₂represents an integer of 0 to 4. In a case where n₂ is 2 or more, Rb₂'spresent in plural number may be the same as or different from eachother, or Rb₂'s present in plural number may be bonded to each other toform a ring.

Examples of the repeating unit which contains a group having the lactonestructure represented by any one of General Formulae (LC1-1) to (LC1-16)include a repeating unit represented by General Formula (AI).

In General Formula (AI), Rb₀ represents a hydrogen atom, a halogen atom,or an alkyl group having 1 to 4 carbon atoms.

Preferred examples of a substituent which may be contained in the alkylgroup of Rb₀ include a hydroxyl group and a halogen atom.

Examples of the halogen atom of Rb₀ include a fluorine atom, a chlorineatom, a bromine atom, and an iodine atom. Rb₀ is preferably a hydrogenatom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking grouphaving a monocyclic or polycyclic alicyclic hydrocarbon structure, anether group, an ester group, a carbonyl group, a carboxyl group, or adivalent group formed by a combination thereof. In particular, Ab ispreferably a single bond or a linking group represented by -Ab₁-CO₂—.Ab₁ is a linear or branched alkylene group or a monocyclic or polycycliccycloalkylene group, and preferably a methylene group, an ethylenegroup, a cyclohexylene group, an adamantylene group, or a norbornylenegroup.

V represents a group represented by any one of General Formulae (LC1-1)to (LC1-16).

In the repeating unit which contains a group containing a lactonestructure, optical isomers are typically present, but any of the opticalisomers may be used. In addition, one optical isomer may be used singly,or a mixture of a plurality of the optical isomers may be used. In acase where one optical isomer is mainly used, the optical purity (ee)thereof is preferably 90 or more, and more preferably 95 or more.

Specific examples of the repeating unit which contains a groupcontaining a lactone structure are shown below, but the presentinvention is not limited thereto.

(In the formula, Rx represents H, CH₃, CH₂OH, or CF₃)

The content of the repeating unit having a lactone group is preferably1% to 65% by mole, more preferably 1% to 30% by mole, still morepreferably 5% to 25% by mole, and particularly preferably 5% to 20% bymole, with respect to all the repeating units of the resin (A).

The resin (A) may further have a repeating unit which contains anorganic group having a polar group, in particular, a repeating unitwhich has an alicyclic hydrocarbon structure substituted with a polargroup.

As a result, substrate adhesiveness and/or developer affinity isimproved. As the alicyclic hydrocarbon structure substituted with apolar group, an adamantyl group, a diamantyl group, or a norbornanegroup is preferable. As the polar group, a hydroxyl group or a cyanogroup is preferable.

Specific examples of the repeating unit having a polar group are shownbelow, but the present invention is not limited thereto.

In a case where the resin (A) includes the repeating unit which containsan organic group having a polar group, the content thereof is preferably1% to 50% by mole, more preferably 1% to 30% by mole, still morepreferably 5% to 25% by mole, and particularly preferably 5% to 20% bymole, with respect to all the repeating units of the resin (A).

Furthermore, as a repeating unit other than the above-describedrepeating units, the resin (A) may include a repeating unit having agroup (photoacid generating group) which generates an acid uponirradiation with actinic rays or radiation. In this case, it can beconsidered that the repeating unit having a photoacid generating groupcorresponds to a compound (B) described below, capable of generating anacid upon irradiation with actinic rays or radiation.

Examples of the repeating unit include a repeating unit represented byGeneral Formula (4).

R₄₁ represents a hydrogen atom or a methyl group. L⁴¹ represents asingle bond or a divalent linking group. L⁴² represents a divalentlinking group. W represents a structural unit capable of decomposing togenerate an acid in a side chain upon irradiation with actinic rays orradiation.

Specific examples of the repeating unit represented by General Formula(4) are shown below, but the present invention is not limited thereto.

Other examples of the repeating unit represented by General Formula (4)include repeating units described in paragraphs [0094] to [0105] ofJP2014-041327A.

In a case where the resin (A) contains the repeating unit having aphotoacid generating group, the content of the repeating unit having aphotoacid generating group is preferably 1 to 40% by mole, morepreferably 5 to 35% by mole, and still more preferably 5 to 30% by mole,with respect to all the repeating units of the resin (A).

The resin (A) can be synthesized using an ordinary method (for example,radical polymerization). Examples of the general synthesis methodinclude a batch polymerization method in which a monomer species and aninitiator are dissolved in a solvent, and the solution is heated toperform polymerization, and a dropping polymerization method in which asolution of a monomer species and an initiator are added dropwise to aheated solvent for 1 to 10 hours, with the dropping polymerizationmethod being preferable.

Examples of the reaction solvent include ethers such as tetrahydrofuran,1,4-dioxane, and diisopropyl ether, ketones such as methyl ethyl ketoneand methyl isobutyl ketone, ester solvents such as ethyl acetate, amidesolvents such as dimethyl formamide and dimethylacetamide, and solventsfor dissolving an actinic ray-sensitive or radiation-sensitive resincomposition, such as propylene glycol monomethyl ether acetate,propylene glycol monomethyl ether, and cyclohexanone, which will bedescribed later. It is preferable that the same solvent as that used inthe actinic ray-sensitive or radiation-sensitive resin composition isused to perform polymerization. With such a use of the solvents,particle generation during storage can be suppressed.

It is preferable that the polymerization reaction is carried out in aninert gas atmosphere such as nitrogen and argon. In order to initiatethe polymerization, a commercially available radical initiator (anazo-based initiator, a peroxide, and the like) is used as thepolymerization initiator. As the radical initiator, an azo-basedinitiator is preferable, and an azo-based initiator having an estergroup, a cyano group, or a carboxyl group is preferable. Preferredexamples of the initiator include azobisisobutyronitrile,azobisdimethylvaleronitrile, and dimethyl2,2′-azobis(2-methylpropionate). The initiator is added or added inportionwise, depending on the purposes, and after completion of thereaction, the reaction product is poured into a solvent, and then adesired polymer is recovered by a method such as powder or solidrecovery. The concentration of a reactant is 5% to 50% by mass, andpreferably 10% to 30% by mass.

The reaction temperature is usually 10° C. to 150° C., preferably 30° C.to 120° C., and still more preferably 60° C. to 100° C.

For purification, a typical method such as a liquid-liquid extractionmethod in which residual monomers and oligomer components are removed bycombining water washing with an appropriate solvent, a purificationmethod in a solid state such as ultrafiltration in which substanceshaving a specific molecular weight or less are removed by filtration, areprecipitation method in which residual monomers are removed bydropping a resin solution over a poor solvent to solidify the resin inthe poor solvent, and a purification method in a solid state in which aresin slurry separated by filtration is washed with a poor solvent canbe applied.

The weight-average molecular weight of the resin (A) is preferably 1,000to 200,000, more preferably 3,000 to 20,000, and still more preferably5,000 to 15,000 as a value in terms of polystyrene by a GPC method. Byadjusting the weight-average molecular weight to 1,000 to 200,000,deterioration in heat resistance or dry etching resistance can beprevented, and deterioration in developability or deterioration in filmforming properties caused by an increase in viscosity can also beprevented.

In another particularly preferred embodiment, the weight-averagemolecular weight of the resin (A) is 3,000 to 9,500 as a value in termsof polystyrene by a GPC method. By adjusting the weight-averagemolecular weight to 3,000 to 9,500, in particular, a resist residue(hereinafter also referred to as “scum”) is suppressed, and a moresatisfactory pattern can thus be formed.

A dispersity (molecular weight distribution) in the range of usually 1to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and particularlypreferably 1.2 to 2.0 is used. As the dispersity decreases, a resolutionand a resist shape are improved, and further, a side wall of a resistpattern is smooth and roughness properties are excellent.

In the actinic ray-sensitive or radiation-sensitive resin composition,the content of the resin (A) is preferably 50% to 99.9% by mass and morepreferably 60% to 99.0% by mass with respect to the total solid contentof the composition.

In addition, in the actinic ray-sensitive or radiation-sensitive resincomposition, the resin (A) may be used singly or in combination of aplurality of the resins (A).

In addition, the resin (A) may include a repeating unit represented byGeneral Formula (VI).

In General Formula (VI),

R₆₁, R₆₂, and R₆₃ each independently represent a hydrogen atom, an alkylgroup, a cycloalkyl group, a halogen atom, a cyano group, or analkoxycarbonyl group. Here, R₆₂ may be bonded to Ar₆ to form a ring, andin this case, R₆₂ represents a single bond or an alkylene group.

X₆ represents a single bond, —COO—, or —CONR₆₄—. R₆₄ represents ahydrogen atom or an alkyl group.

L₆ represents a single bond or an alkylene group.

Ar₆ represents a (n+1)-valent aromatic ring group, and in a case whereAr₆ is bonded to R₆₂ to form a ring, Ar₆ represents a (n+2)-valentaromatic ring group.

In a case of n≥2, Y₂'s each independently represent a hydrogen atom or agroup capable of leaving by the action of an acid, provided that atleast one of Y₂'s represents a group capable of leaving by the action ofan acid.

n represents an integer of 1 to 4.

As the group capable of leaving by the action of an acid represented byY₂, a structure represented by General Formula (VI-A) is morepreferable.

Here, L₁ and L₂ each independently represent a hydrogen atom, an alkylgroup, a cycloalkyl group, an aryl group, or a group formed by acombination of an alkylene group and an aryl group.

M represents a single bond or a divalent linking group.

Q represents an alkyl group, a cycloalkyl group which may have aheteroatom, an aryl group which may have a heteroatom, an amino group,an ammonium group, a mercapto group, a cyano group, or an aldehydegroup.

At least two of Q, M, or L₁ may be bonded to each other to form a ring(preferably a 5- or 6-membered ring).

The repeating unit represented by General Formula (VI) is preferably arepeating unit represented by General Formula (3).

In General Formula (3),

Ar₃ represents an aromatic ring group.

R₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, anaryl group, an aralkyl group, an alkoxy group, an acyl group, or aheterocyclic group.

M₃ represents a single bond or a divalent linking group.

Q₃ represents an alkyl group, a cycloalkyl group, an aryl group, or aheterocyclic group.

At least two of Q₃, M₃, or R₃ may be bonded to each other to form aring.

The aromatic ring group represented by Ar₃ is the same as Ar₆ in GeneralFormula (VI) in a case where n in General Formula (VI) represents 1. Inthis case, a phenylene group or a naphthylene group is preferable, and aphenylene group is more preferable.

Specific examples of the repeating unit represented by General Formula(VI) are shown below, but the present invention is not limited thereto.

It is also preferable that the resin (A) includes a repeating unitrepresented by General Formula (4).

In General Formula (4),

R₄₁, R₄₂, and R₄₃ each independently represent a hydrogen atom, an alkylgroup, a cycloalkyl group, a halogen atom, a cyano group, or analkoxycarbonyl group. R₄₂ may be bonded to L₄ to form a ring, and inthis case, R₄₂ represents an alkylene group.

L₄ represents a single bond or a divalent linking group. In a case whereL₄ and R₄₂ form a ring, L₄ represents a trivalent linking group.

R₄₄ and R₄₅ represent a hydrogen atom, an alkyl group, a cycloalkylgroup, an aryl group, an aralkyl group, an alkoxy group, an acyl group,or a heterocyclic group.

M₄ represents a single bond or a divalent linking group.

Q₄ represents an alkyl group, a cycloalkyl group, an aryl group, or aheterocyclic group.

At least two of Q₄, M₄, or R₄₄ may be bonded to each other to form aring.

R₄₁, R₄₂, and R₄₃ have the same definitions and the same preferableranges as R₅₁, R₅₂, and R₅₃ in General Formula (V).

L₄ has the same definition and the same preferable range as L₅ inGeneral Formula (V). R₄₄ and R₄₅ have the same definitions and the samepreferable ranges as R₃ in General Formula (3).

M₄ has the same definition and the same preferable range as M₃ inGeneral Formula (3).

Q₄ has the same definition and the same preferable range as Q₃ inGeneral Formula (3). Examples of a ring which is formed by at least twoof Q₄, M₄, or R₄₄ being bonded to each other include the ring which isformed by at least two of Q₃, M₃, or R₃ being bonded to each other, andpreferable ranges thereof are also the same.

Specific examples of the repeating unit represented by General Formula(4) are shown below, but the present invention is not limited thereto.

In addition, the resin (A) may include a repeating unit represented byGeneral Formula (BZ).

In General Formula (BZ), AR represents an aryl group. Rn represents analkyl group, a cycloalkyl group, or an aryl group. Rn and AR may bebonded to each other to form a non-aromatic ring.

R₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, ahalogen atom, a cyano group, or an alkyloxycarbonyl group.

Specific examples of the repeating unit represented by General Formula(BZ) are shown below, but the present invention is not limited thereto.

The repeating unit having an acid-decomposable group may be used singlyor in combination of two or more kinds thereof.

The content of the repeating unit having an acid-decomposable group inthe resin (A) (in a case where the resin (A) includes a plurality ofrepeating units having an acid-decomposable group, the total contentthereof) is preferably from 5% by mole to 80% by mole, more preferablyfrom 5% by mole to 75% by mole, and still more preferably from 10% bymole to 65% by mole, with respect to all the repeating units of theresin (A).

The resin (A) may contain a repeating unit represented by GeneralFormula (V) or General Formula (VI).

In the formulae,

R₆ and R₇ each independently represent a hydrogen atom, a hydroxylgroup, a linear, branched, or cyclic alkyl group having 1 to 10 carbonatoms, an alkoxy group or acyloxy group, a cyano group, a nitro group,an amino group, a halogen atom, an ester group (—OCOR or —COOR: Rrepresents an alkyl group having 1 to 6 carbon atoms or a fluorinatedalkyl group), or a carboxyl group.

n₃ represents an integer of 0 to 6. n₄ represents an integer of 0 to 4.

X₄ is a methylene group, an oxygen atom, or a sulfur atom.

Specific examples of the repeating unit represented by General Formula(V) or General Formula (VI) are shown below, but the present inventionis not limited thereto.

The resin (A) may further have a repeating unit having a silicon atom ina side chain. Examples of the repeating unit having a silicon atom in aside chain include a (meth)acrylate-based repeating unit having asilicon atom and a vinyl-based repeating unit having a silicon atom. Therepeating unit having a silicon atom in a side chain is usually arepeating unit having a group having a silicon atom in a side chain.Examples of the group having a silicon atom include a trimethylsilylgroup, a triethylsilyl group, a triphenylsilyl group, atricyclohexylsilyl group, a tristrimethylsiloxysilyl group, atristrimethylsilylsilyl group, a methylbistrimethylsilylsilyl group, amethylbistrimethylsiloxysilyl group, a dimethyltrimethylsilylsilylgroup, a dimethyltrimethylsiloxysilyl group, a cyclic or linearpolysiloxane, and a cage-type or ladder-type or random-typesilsesquioxane structure as described below. In the formulae, R and R¹each independently represent a monovalent substituent. * represents abond.

Suitable examples of the repeating units having the above-mentionedgroup include a repeating unit derived from an acrylate or methacrylatecompound having the above-mentioned group, and a repeating unit derivedfrom compound having the above-mentioned group and a vinyl group.

The repeating unit having a silicon atom is preferably a repeating unithaving a silsesquioxane structure, whereby it is possible to express avery excellent collapse performance in the formation of an ultrafinepattern (for example, a pattern with a line width of 50 nm or less)having a cross-sectional shape of a high aspect ratio (for example, aratio of film thickness/line width of 3 or more).

Examples of the silsesquioxane structure include a cage-typesilsesquioxane structure, a ladder-type silsesquioxane structure, and arandom-type silsesquioxane structure. Among those, preferred is acage-type silsesquioxane structure.

Here, the cage-type silsesquioxane structure is a silsesquioxanestructure having a cage-shaped skeleton. The cage-type silsesquioxanestructure may be a complete cage-type silsesquioxane structure or anincomplete cage-type silsesquioxane structure, with the completecage-type silsesquioxane structure being preferable.

Furthermore, the ladder-type silsesquioxane structure is asilsesquioxane structure having a ladder-shaped skeleton.

In addition, the random-type silsesquioxane structure is asilsesquioxane structure whose skeleton is of random.

The cage-type silsesquioxane structure is preferably a siloxanestructure represented by Formula (S).

In Formula (S), R represents a monovalent organic group. R's present inplural number may be the same as or different from each other.

The organic group is not particularly limited, but specific examplesthereof include a hydrocarbon group which may have a hydroxyl group, anitro group, a carboxy group, an alkoxy group, an amino group, amercapto group, a blocked mercapto group (for example, an acylgroup-blocked (protected) mercapto group), an acyl group, an imidogroup, a phosphino group, a phosphinyl group, a silyl group, a vinylgroup, or a heteroatom, a (meth)acrylic group-containing group, and anepoxy group-containing group.

Examples of the heteroatom in the hydrocarbon group which may have aheteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and aphosphorus atom.

Examples of the hydrocarbon group which may have a heteroatom include analiphatic hydrocarbon group, an aromatic hydrocarbon group, and a groupformed by a combination of these groups.

The aliphatic hydrocarbon group may be linear, branched or cyclic.Specific examples of the aliphatic hydrocarbon group include a linear orbranched alkyl group (in particular, having 1 to 30 carbon atoms), alinear or branched alkenyl group (in particular, having 2 to 30 carbonatoms), and a linear or branched alkynyl group (in particular, having 2to 30 carbon atoms).

Examples of the aromatic hydrocarbon group include aromatic hydrocarbongroups having 6 to 18 carbon atoms, such as a phenyl group, a tolylgroup, a xylyl group, and a naphthyl group.

In the case where the resin (A) has a repeating unit having a siliconatom in the side chain, the content thereof is preferably 1% to 30% bymole, more preferably 5% to 25% by mole, and still more preferably 5% to20% by mole, with respect to all repeating units in the resin (A).

(B) Compound (Photoacid Generator) Capable of Generating Acid by ActinicRays or Radiation

It is preferable that the actinic ray-sensitive or radiation-sensitiveresin composition contains a compound (hereinafter also referred to as a“photoacid generator <<PAG>>”) capable of generating an acid by actinicrays or radiation.

The photoacid generator may be in a form of a low molecular compound orin a form introduced into a part of a polymer. Further, a combination ofthe form of a low molecular compound and the form introduced into a partof a polymer may also be used.

In a case where the photoacid generator is in the form of a lowmolecular compound, the molecular weight thereof is preferably 3,000 orless, more preferably 2,000 or less, and still more preferably 1,000 orless.

In a case where the photoacid generator is included in a part of apolymer, it may be included in a part of the resin (A) or in a resinother than the resin (A).

In the present invention, it is preferable that the photoacid generatoris in the form of a low molecular compound.

The photoacid generator is not particularly limited as long as it is aknown photoacid generator, but the photoacid generator is preferably acompound capable of generating an organic acid, for example, at leastone of sulfonic acid, bis(alkylsulfonyl)imide, ortris(alkylsulfonyl)methide, upon irradiation with actinic rays orradiation, and preferably electron beams or extreme ultraviolet rays.

More preferred examples of the photoacid generator include a compoundrepresented by General Formula (ZI), (ZII), or (ZIII).

In General Formula (ZI),

R₂₀₁, R₂₀₂, and R₂₀₃ each independently represent an organic group.

The number of carbon atoms in the organic group as R₂₀₁, R₂₀₂, and R₂₀₃is generally 1 to 30, and preferably 1 to 20.

In addition, two out of R₂₀₁ to R₂₀₃ may be bonded to each other to forma ring structure, and the ring may contain therein an oxygen atom, asulfur atom, an ester bond, an amide bond, or a carbonyl group. Examplesof the group formed by the bonding of two of R₂₀₁ to R₂₀₃ include analkylene group (for example, a butylene group and a pentylene group).

Z⁻ represents a non-nucleophilic anion (anion having an extremely lowability of causing a nucleophilic reaction).

Examples of the non-nucleophilic anion include a sulfonate anion (suchas an aliphatic sulfonate anion, an aromatic sulfonate anion, and acamphor sulfonate anion), a carboxylate anion (such as an aliphaticcarboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion), a sulfonylimide anion, a bis(alkylsulfonyl)imideanion, and a tris(alkylsulfonyl)methide anion.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphaticcarboxylate anion may be an alkyl group or a cycloalkyl group, andpreferred examples thereof include a linear or branched alkyl grouphaving 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbonatoms.

Preferred examples of the aromatic group in the aromatic sulfonate anionand the aromatic carboxylate anion include an aryl group having 6 to 14carbon atoms, such as a phenyl group, a tolyl group, and a naphthylgroup.

The alkyl group, the cycloalkyl group, and the aryl group exemplifiedabove may have a substituent. Specific examples of the substituentinclude a nitro group, a halogen atom such as fluorine atom, a carboxylgroup, a hydroxyl group, an amino group, a cyano group, an alkoxy group(preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferablyhaving 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbonatoms), an acyl group (preferably having 2 to 12 carbon atoms), analkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), analkylthio group (preferably having 1 to 15 carbon atoms), analkylsulfonyl group (preferably having 1 to 15 carbon atoms), analkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), anaryloxysulfonyl group (preferably having 6 to 20 carbon atoms), analkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), acycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbonatoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbonatoms), and a cycloalkylalkyloxyalkyloxy group (preferably having 8 to20 carbon atoms).

The aryl group or the ring structure which is contained in each groupmay further have an alkyl group (preferably having 1 to 15 carbon atoms)as a substituent.

Preferred examples of the aralkyl group in the aralkyl carboxylate anioninclude an aralkyl group having 7 to 12 carbon atoms, such as a benzylgroup, a phenethyl group, a naphthylmethyl group, a naphthylethyl group,and a naphthylbutyl group.

Examples of the sulfonylimide anion include a saccharin anion.

The alkyl group in the bis(alkylsulfonyl)imide anion and thetris(alkylsulfonyl)methide anion is preferably an alkyl group having 1to 5 carbon atoms. Examples of the substituent of this alkyl groupinclude a halogen atom, a halogen atom-substituted alkyl group, analkoxy group, an alkylthio group, an alkyloxysulfonyl group, anaryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, with thefluorine atom and the fluorine atom-substituted alkyl group beingpreferable.

In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion maybe bonded to each other to form a ring structure. Thus, the acidstrength is increased.

Other examples of the non-nucleophilic anion include fluorinatedphosphorus (for example, PF₆ ⁻), fluorinated boron (for example, BF₄ ⁻),and fluorinated antimony (for example, SbF₆ ⁻).

The non-nucleophilic anion is preferably an aliphatic sulfonate anionsubstituted with a fluorine atom at least at the α-position of thesulfonic acid, an aromatic sulfonate anion substituted with a fluorineatom or a fluorine atom-containing group, a bis(alkylsulfonyl)imideanion in which the alkyl group is substituted with a fluorine atom, or atris(alkylsulfonyl)methide anion in which the alkyl group is substitutedwith a fluorine atom. The non-nucleophilic anion is more preferably aperfluoroaliphatic sulfonate anion (still more preferably having 4 to 8carbon atoms) or a fluorine atom-containing benzenesulfonate anion, andstill more preferably a nonafluorobutanesulfonate anion, aperfluorooctanesulfonate anion, a pentafluorobenzenesulfonate anion, ora 3,5-bis(trifluoromethyl)benzenesulfonate anion.

From the viewpoint of the acid strength, it is preferable that the pKaof the acid generated is −1 or less so as to improve the sensitivity.

Moreover, an anion represented by General Formula (AN1) may also bementioned as a preferred embodiment of the non-nucleophilic anion.

In the formula,

Xf's each independently represent a fluorine atom or an alkyl groupsubstituted with at least one fluorine atom.

R¹ and R² each independently represent a hydrogen atom, a fluorine atom,or an alkyl group, and in a case where R¹'s and R²'s are present inplural numbers, R¹'s and R²'s may be the same as or different from eachother.

L represents a divalent linking group, and in a case where L's arepresent in plural number, L's may be the same as or different from eachother.

A represents a cyclic organic group.

x represents an integer of 1 to 20, y represent an integer of 0 to 10,and z represents an integer of 0 to 10.

General Formula (AN1) will be described in more detail.

As the alkyl group in the alkyl group substituted with a fluorine atomof Xf, an alkyl group having 1 to 10 carbon atoms is preferable, and analkyl group having 1 to 4 carbon atoms is more preferable. In addition,as the alkyl group in the alkyl group substituted with a fluorine atom,of Xf, a perfluoroalkyl group is preferable.

Xf is preferably a fluorine atom or a perfluoroalkyl group having or 1to 4 carbon atoms. Specific examples of Xf include a fluorine atom, CF₃,C₂F₅, C₃F₇, C₄F₉, CH₂CF₃, CH₂CH₂CF₃, CH₂C₂F₅, CH₂CH₂C₂F₅, CH₂C₃F₇,CH₂CH₂C₃F₇, CH₂C₄F₉, and CH₂CH₂C₄F₉. Among these, a fluorine atom or CF₃is preferable.

In particular, it is preferable that both Xf's are a fluorine atom.

The alkyl group of R¹ and R² may have a substituent (preferably afluorine atom), and an alkyl group having 1 to 4 carbon atoms ispreferable. A perfluoroalkyl group having 1 to 4 carbon atoms is morepreferable. Specific examples of the alkyl group having a substituent ofR¹ and R² include CF₃, C₂F₅, C₃F₇, C₄F₉, C₅F₁₁, C₆F₁₃, C₇F₁₅, C₈F₁₇,CH₂CF₃, CH₂CH₂CF₃, CH₂C₂F₅, CH₂CH₂C₂F₅, CH₂C₃F₇, CH₂CH₂C₃F₇, CH₂C₄F₉,and CH₂CH₂C₄F₉. Among these, CF₃ is preferable.

R¹ and R² are preferably a fluorine atom or CF₃.

x is preferably 1 to 10, and more preferably 1 to 5.

y is preferably 0 to 4, and more preferably 0.

z is preferably 0 to 5, and more preferably 0 to 3.

The divalent linking group of L is not particularly limited, andexamples thereof include —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO₂—, analkylene group, a cycloalkylene group, an alkenylene group, a linkinggroup obtained by linking a plurality of these groups to each other,with the linking group having 12 or less carbon atoms in total beingpreferable. Among these, —COO—, —OCO—, —CO—, or —O— is preferable, and—COO— or —OCO— is more preferable.

In General Formula (ANI), preferred examples of a combination of partialstructures other than A include SO³⁻—CF₂—CH₂—OCO—,SO³⁻—CF₂—CHF—CH₂—OCO—, SO³⁻—CF₂—OCO—, SO³⁻—CF₂—CF₂—CH₂—, andSO³⁻—CF₂—CH(CF₃)—OCO—.

The cyclic organic group of A is not particularly limited as long as ithas a cyclic structure, and examples thereof include an alicyclic group,an aryl group, a heterocyclic group (including not only an aromaticheterocyclic group but also a non-aromatic heterocyclic group).

The alicyclic group may be monocyclic or polycyclic, and amonocycloalkyl group such as a cyclopentyl group, a cyclohexyl group,and a cyclooctyl group, or a polycycloalkyl group such as a norbornylgroup, a tricyclodecanyl group, a tetracyclodecanyl group, atetracyclododecanyl group, and an adamantyl group is preferable. Amongthese, an alicyclic group with a bulky structure, having 7 or morecarbon atoms, such as a norbornyl group, a tricyclodecanyl group, atetracyclodecanyl group, a tetracyclododecanyl group, and an adamantylgroup is preferable from the viewpoints of suppressing in-film diffusionin a heating step after exposure and improving a mask error enhancementfactor (MEEF).

Examples of the aryl group include a benzene ring, a naphthalene ring, aphenanthrene ring, and an anthracene ring.

Examples of the heterocyclic group include a furan ring, a thiophenering, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, adibenzothiophene ring, and a group derived from a pyridine ring. Amongthese, a furan ring, a thiophene ring, or a group derived from apyridine ring is preferable.

Moreover, examples of the cyclic organic group include a lactonestructure, and specific examples thereof include lactone structuresrepresented by General Formulae (LC1-1) to (LC1-17).

The cyclic organic group may have a substituent, and examples of thesubstituent include an alkyl group (which may be linear, branched, orcyclic, and preferably has 1 to 12 carbon atoms), a cycloalkyl group(which may be any of a monocycle, a polycycle, or a Spiro ring, andpreferably has 3 to 20 carbon atoms), an aryl group (which may belinear, branched, or aryl, and preferably has 6 to 14 carbon atoms), ahydroxyl group, an alkoxy group, an ester group, an amido group, aurethane group, an ureido group, a thioether group, a sulfonamide group,and a sulfonate group. Incidentally, the carbon (carbon contributing toring formation) constituting the cyclic organic group may be carbonylcarbon.

Furthermore, the substituent corresponds to Rb₂ in (LC1-1) to (LC1-17).Further, in (LC1-1) to (LC1-17), n₂ represents an integer of 0 to 4. Ina case where n₂ is 2 or more, Rb₂'s which are present in plural numbermay be the same as or different from each other, and Rb₂'s which arepresent in plural number may be bonded to each other to form a ring.

In General Formula (ZI), examples of the organic group of R₂₀₁, R₂₀₂,and R₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group.

It is preferable that at least one of R₂₀₁, R₂₀₂, or R₂₀₃ is an arylgroup, and it is more preferable that all of R₂₀₁, R₂₀₂, or R₂₀₃represent an aryl group. As the aryl group, not only a phenyl group or anaphthyl group but also a heteroaryl group such as an indole residue ora pyrrole residue may be used. As the alkyl group and the cycloalkylgroup of R₂₀₁ to R₂₀₃, a linear or branched alkyl group having 1 to 10carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms ispreferable. As the alkyl group, a methyl group, an ethyl group, an-propyl group, an i-propyl group, or a n-butyl group is morepreferable. As the cycloalkyl group, a cyclopropyl group, a cyclobutylgroup, a cyclopentyl group, a cyclohexyl group, or a cycloheptyl groupis more preferable. Each of the groups may further have a substituent.Examples of the substituent include a nitro group, a halogen atom suchas a fluorine atom, a carboxyl group, a hydroxyl group, an amino group,a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms),a cycloalkyl group (preferably having 3 to 15 carbon atoms), an arylgroup (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group(preferably having 2 to 7 carbon atoms), an acyl group (preferablyhaving 2 to 12 carbon atoms), and an alkoxycarbonyloxy group (preferablyhaving 2 to 7 carbon atoms), but the present invention is not limitedthereto.

Next, General Formulae (ZII) and (ZIII) will be described.

In General Formulae (ZII) and (ZIII), R₂₀₄ to R₂₀₇ each independentlyrepresent an aryl group, an alkyl group, or a cycloalkyl group.

As the aryl group of R₂₀₄ to R₂₀₇, a phenyl group or a naphthyl group ispreferable, and a phenyl group is more preferable. The aryl group ofR₂₀₄ to R₂₀₇ may be an aryl group having a heterocyclic structure havingan oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples ofthe framework of the aryl group having a heterocyclic structure includepyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

Preferred examples of the alkyl group and the cycloalkyl group for R₂₀₄to R₂₀₇ include a linear or branched alkyl group having 1 to 10 carbonatoms (for example, a methyl group, an ethyl group, a propyl group, abutyl group, and a pentyl group) and a cycloalkyl group having 3 to 10carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, anda norbornyl group).

The aryl group, the alkyl group, and the cycloalkyl group of R₂₀₄ toR₂₀₇ may have a substituent, and examples of the substituent which maybe contained in the aryl group, the alkyl group, and the cycloalkylgroup of R₂₀₄ to R₂₀₇ include an alkyl group (for example, an alkylgroup having 1 to 15 carbon atoms), a cycloalkyl group (for example, acycloalkyl group having 3 to 15 carbon atoms), an aryl group (forexample, an aryl group having 6 to 15 carbon atoms), an alkoxy group(for example, an alkoxy group having 1 to 15 carbon atoms), a halogenatom, a hydroxyl group, and a phenylthio group.

Furthermore, in General Formula (ZII), Z⁻ represents a non-nucleophilicanion, and specifically, it has the same definition and the samepreferred embodiment as the one described as Z⁻ in General Formula (ZI).

Specific examples of General Formulae (ZI) to (ZIII) are shown below,but are not limited thereto.

In the present invention, from the viewpoint of suppressing diffusion ofan acid generated by exposure to a non-exposed area and improvingresolution, the photoacid generator is preferably a compound whichgenerates an acid (more preferably sulfonic acid) having a volume of 130Å³ or more upon irradiation with electron beams or extreme ultravioletrays, more preferably a compound which generates an acid (morepreferably sulfonic acid) having a volume of 190 Å³ or more, still morepreferably a compound which generates an acid (more preferably sulfonicacid) having a volume of 270 Å³ or more, and particularly preferably acompound which generates an acid (more preferably sulfonic acid) havinga volume of 400 Å³ or more. From the viewpoints of sensitivity andcoating solvent solubility, the volume is preferably 2,000 Å³ or less,and more preferably 1,500 Å³ or less. A value of the volume is obtainedusing “WinMOPAC” manufactured by FUJITSU. That is, a chemical structureof an acid according to each example is input, and then the most stableconformation of each acid is determined through a molecular fieldcalculation using a MM3 method with the input chemical structure as aninitial structure. Next, a molecular orbital calculation is carried outon the most stable conformation using a PM3 method, and as a result,“accessible volume” of each acid can be calculated. Further, 1 Å³ means0.1 nm.

In the present invention, the photoacid generators capable of generatingan acid exemplified below upon irradiation with actinic rays orradiation are preferable. In some of the examples, a calculated value ofthe volume is added (unit: Å³). Further, the value as calculated hereinis a value of the volume of an acid in which a proton is bonded to theanion portion.

With regard to the photoacid generator, reference can be made toparagraphs [0368] to [0377] of JP2014-41328A and paragraphs [0240] to[0262] of JP2013-228681A (paragraph [0339] of the correspondingUS2015/004533A), the content of which is incorporated herein byreference. In addition, specific preferred examples include, but are notlimited to, the following compounds.

The photoacid generator may be used singly or in combination of two ormore kinds thereof.

The content of the photoacid generator in the actinic ray-sensitive orradiation-sensitive resin composition is preferably 0.1% to 50% by mass,more preferably 5% to 50% by mass, and still more preferably 8% to 40%by mass with respect to the total solid content of the composition. Inparticular, in order to simultaneously realize high sensitivity and highresolution upon irradiation of electron beams or extreme ultravioletrays, the content of the photoacid generator is preferably high, morepreferably 10% to 40% by mass, and still more preferably 10% to 35% bymass.

(C) Solvent

In order to dissolve the respective components to prepare the actinicray-sensitive or radiation-sensitive resin composition, a solvent can beused. Examples of the solvent used include organic solvents such asalkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkylether, alkyl lactate, alkyl alkoxy propionate, cyclic lactone having 4to 10 carbon atoms, a monoketone compound having 4 to 10 carbon atoms,which may include a ring, alkylene carbonate, alkyl alkoxy acetate, andalkyl pyruvate,

As the alkylene glycol monoalkyl ether carboxylate, for example,propylene glycol monomethyl ether acetate, propylene glycol monoethylether acetate, propylene glycol propyl ether acetate, propylene glycolmonobutyl ether acetate, propylene glycol monomethyl ether propionate,propylene glycol monoethyl ether propionate, ethylene glycol monomethylether acetate, or ethylene glycol monoethyl ether acetate is preferable.

As the alkylene glycol monoalkyl ether, for example, propylene glycolmonomethyl ether, propylene glycol monoethyl ether, propylene glycolmonopropyl ether, propylene glycol monobutyl ether, ethylene glycolmonomethyl ether, or ethylene glycol monoethyl ether is preferable.

As the alkyl lactate, for example, methyl lactate, ethyl lactate, propyllactate, or butyl lactate is preferable.

As the alkyl alkoxy propionate, for example, 3-ethyl ethoxypropionate,3-methyl methoxypropionate, 3-methyl ethoxypropionate, or ethyl3-methoxypropionate is preferable.

As the cyclic lactone having 4 to 10 carbon atoms, for example,β-propiolactone, β-butyrolactone, γ-butyrolactone,α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone,γ-caprolactone, γ-octanoic lactone, or α-hydroxy-γ-butyrolactone ispreferable.

As the monoketone compound having 4 to 10 carbon atoms, which maycontain a ring, for example, 2-butanone, 3-methylbutanone, pinacolone,2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone,2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone,2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone,3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone,2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone,2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone,3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone,2-methylcyclopentanone, 3-methylcyclopentanone,2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone,cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone,4-ethylcyclohexanone, 2,2-dimethylcyclohexanone,2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone,2-methylcycloheptanone, or 3-methylcycloheptanone is preferable.

As the alkylene carbonate, for example, propylene carbonate, vinylenecarbonate, ethylene carbonate, or butylene carbonate is preferable.

As the alkyl alkoxyacetate, for example, 2-methoxyethyl acetate,2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate,3-methoxy-3-methylbutyl acetate, or 1-methoxy-2-propyl acetate ispreferable.

As the alkyl pyruvate, for example, methyl pyruvate, ethyl pyruvate, orpropyl pyruvate is preferable.

Examples of the solvent which can be preferably used include a solventhaving a boiling point of 130° C. or more at a normal temperature undera normal pressure. Specific examples of the solvent includecyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethyleneglycol monoethyl ether acetate, propylene glycol monomethyl etheracetate, 3-ethyl ethoxypropionate, ethyl pyruvate, 2-ethoxyethylacetate, 2-(2-ethoxyethoxy)ethyl acetate, and propylene carbonate.

In the present invention, the solvents may be used singly or incombination of two or more kinds thereof.

In the present invention, as the organic solvent, a mixed solvent inwhich a solvent containing a hydroxyl group in a structure is mixed witha solvent containing no hydroxyl group may be used.

Examples of the solvent containing a hydroxyl group include ethyleneglycol, ethylene glycol monomethyl ether, ethylene glycol monoethylether, propylene glycol, propylene glycol monomethyl ether, propyleneglycol monoethyl ether, and ethyl lactate, and among these, propyleneglycol monomethyl ether or ethyl lactate is preferable.

Examples of the solvent containing no hydroxyl group include propyleneglycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone,γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone,N,N-dimethylacetamide, and dimethyl sulfoxide, and among these,propylene glycol monomethyl ether acetate, ethyl ethoxypropionate,2-heptanone, γ-butyrolactone, cyclohexanone, or butyl acetate ispreferable, and propylene glycol monomethyl ether acetate, ethylethoxypropionate, or 2-heptanone is more preferable.

A mixing ratio of the solvent containing a hydroxyl group to the solventcontaining no hydroxyl group is preferably 1/99 to 99/1, more preferably10/90 to 90/10, and still more preferably 20/80 to 60/40 by mass. Inparticular, a mixed solvent containing 50% by mass or more of thesolvent containing no hydroxyl group is preferable from the viewpoint ofcoating uniformity.

It is preferable that the solvent is a mixed solvent containing two ormore propylene glycol monomethyl ether acetates.

As the solvent, for example, the solvents described in paragraphs 0013to 0029 of JP2014-219664A can also be used.

(E) Basic Compound

In order to reduce a change in performance with the lapse of time fromexposure to heating, it is preferable that the actinic ray-sensitive orradiation-sensitive resin composition includes a basic compound (E).

Preferred examples of the basic compound include compounds havingstructures represented by General Formulae (A) to (E).

In General Formulae (A) and (E), R²⁰⁰, R²⁰¹, and R²⁰² may be the same asor different from each other and each independently represent a hydrogenatom, an alkyl group (preferably having 1 to 20 carbon atoms), acycloalkyl group (preferably having 3 to 20 carbon atoms), or an arylgroup (preferably having 6 to 20 carbon atoms). Here, R²⁰¹ and R²⁰² maybe bonded to each other to form a ring.

As the alkyl group having a substituent, an aminoalkyl group having 1 to20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or acyanoalkyl group having 1 to 20 carbon atoms is preferable.

R²⁰³, R²⁰⁴, R²⁰⁵, and R²⁰⁶ may be the same as or different from eachother and each independently represent an alkyl group having 1 to 20carbon atoms.

It is more preferable that the alkyl group in General Formulae (A) and(E) is unsubstituted.

Preferred examples of the compound include, in addition to guanidine,aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine,aminoalkylmorpholine, and piperidine, a compound having an imidazolestructure, a diazabicyclo structure, an onium hydroxide structure, anonium carboxylate structure, a trialkylamine structure, an anilinestructure, or a pyridine structure, an alkylamine derivative having ahydroxyl group and/or an ether bond, and an aniline derivative having ahydroxyl group and/or an ether bond.

Examples of the compound having an imidazole structure includeimidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of thecompound having a diazabicyclo structure include1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nona-5-ene, and1,8-diazabicyclo[5,4,0]undeca-7-ene. Examples of the compound having anonium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group,and specific examples thereof include triphenylsulfonium hydroxide,tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodoniumhydroxide, phenacyl thiophenium hydroxide, and 2-oxopropylthiopheniumhydroxide. The compound having an onium carboxylate structure is acompound obtained by carboxylation of the anionic moiety of a compoundhaving an onium hydroxide structure, and examples thereof includeacetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate.Examples of the compound having trialkylamine structure includetri-(n-butyl)amine and tri-(n-octyl)amine. Examples of the compoundhaving an aniline structure include 2,6-diisopropylaniline,N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline.Examples of the alkylamine derivative having a hydroxyl group and/or anether bond include ethanolamine, diethanolamine, triethanolamine, andtris(methoxyethoxyethyl)amine. Examples of the aniline derivative havinga hydroxyl group and/or an ether bond includeN,N-bis(hydroxyethyl)aniline.

Preferred examples of the basic compound also include an amine compoundhaving a phenoxy group and an ammonium salt compound having a phenoxygroup.

As the amine compound, a primary, secondary, or tertiary amine compoundcan be used, and an amine compound in which at least one alkyl group isbonded to a nitrogen atom is preferable. It is more preferable that theamine compound is a tertiary amine compound. In the amine compound, aslong as at least one alkyl group (preferably having 1 to 20 carbonatoms) is bonded to a nitrogen atom, in addition to the alkyl group, acycloalkyl group (preferably having 3 to 20 carbon atoms) or an arylgroup (preferably 6 to 12 carbon atoms) may be bonded to a nitrogenatom.

In addition, it is preferable that the amine compound has an oxygen atomat an alkyl chain to form an oxyalkylene group. The number ofoxyalkylene groups in a molecule is 1 or more, preferably 3 to 9, andstill more preferably 4 to 6. Among the oxyalkylene groups, anoxyethylene group (—CH₂CH₂O—) or an oxypropylene group (—CH(CH₃)CH₂O— or—CH₂CH₂CH₂O—) is preferable, and an oxyethylene group is morepreferable.

As the ammonium salt compound, a primary, secondary, tertiary, orquaternary ammonium salt compound can be used, and an ammonium saltcompound in which at least one alkyl group is bonded to a nitrogen atomis preferable. In the ammonium salt compound, as long as at least onealkyl group (preferably having 1 to 20 carbon atoms) is bonded to anitrogen atom, in addition to the alkyl group, a cycloalkyl group(preferably having 3 to 20 carbon atoms) or an aryl group (preferably 6to 12 carbon atoms) may be bonded to a nitrogen atom.

In addition, it is preferable that the ammonium salt compound has anoxygen atom at an alkyl chain to form an oxyalkylene group. The numberof oxyalkylene groups is 1 or more, preferably 3 to 9, and still morepreferably 4 to 6 in a molecule. Among the oxyalkylene groups, anoxyethylene group (—CH₂CH₂O—) or an oxypropylene group (—CH(CH₃)CH₂O— or—CH₂CH₂CH₂O—) is preferable, and an oxyethylene group is morepreferable.

Examples of an anion of the ammonium salt compound include a halogenatom, a sulfonate, a borate, and a phosphate, and among these, a halogenatom or a sulfonate is preferable. As the halogen atom, a chloride, abromide, or an iodide is preferable. As the sulfonate, an organicsulfonate having 1 to 20 carbon atoms is preferable. Examples of theorganic sulfonate include an alkyl sulfonate having 1 to 20 carbon atomsand an aryl sulfonate. The alkyl group of the alkyl sulfonate may have asubstituent, and examples of the substituent include fluorine, chlorine,bromine, an alkoxy group, an acyl group, and an aryl group. Specificexamples of the alkyl sulfonate include methane sulfonate, ethanesulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzylsulfonate, trifluoromethane sulfonate, pentafluoromethane sulfonate, andnonafluoromethane sulfonate. Examples of the aryl group of the arylsulfonate include a benzene ring, a naphthalene ring, and an anthracenering. The benzene ring, the naphthalene ring, and the anthracene ringmay have a substituent. As the substituent, a linear or branched alkylgroup having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6carbon atoms is preferable. Specific examples of the linear or branchedalkyl group and the cycloalkyl group include methyl, ethyl, n-propyl,isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, and cyclohexyl. Otherexamples of the substituent include an alkoxy group having 1 to 6 carbonatoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxygroup.

The amine compound having a phenoxy group or the ammonium salt compoundhaving a phenoxy group is an amine compound or an ammonium salt compoundhaving a phenoxy group at a terminal of an alkyl group opposite to anitrogen atom. The phenoxy group may have a substituent. Examples of thesubstituent of the phenoxy group include an alkyl group, an alkoxygroup, a halogen atom, a cyano group, a nitro group, a carboxyl group, acarboxylate group, a sulfonate group, an aryl group, an aralkyl group,an acyloxy group, and an aryloxy group. The substitution position of thesubstituent may be any one of the 2- to 6-positions. The number ofsubstituents is 1 to 5.

It is preferable that at least one oxyalkylene group is present betweena phenoxy group and a nitrogen atom. The number of oxyalkylene groups is1 or more, preferably 3 to 9, and still more preferably 4 to 6 in amolecule. Among the oxyalkylene groups, an oxyethylene group (—CH₂CH₂O—)or an oxypropylene group (—CH(CH₃)CH₂O— or —CH₂CH₂CH₂O—) is preferable,and an oxyethylene group is more preferable.

The amine compound having a phenoxy group can be obtained by heating aprimary or secondary amine having a phenoxy group and a haloalkyl etherto react with each other, adding an aqueous solution of a strong basesuch as sodium hydroxide, potassium hydroxide, and tetraalkylammonium tothe obtained reaction product, and carrying out extraction with anorganic solvent such as ethyl acetate and chloroform. Alternatively, theamine compound having a phenoxy group can be obtained by heating aprimary or secondary amine and haloalkyl ether having a phenoxy group ata terminal to react with each other, adding an aqueous solution of astrong base such as sodium hydroxide, potassium hydroxide, andtetraalkylammonium to the obtained reaction product, and carrying outextraction with an organic solvent such as ethyl acetate and chloroform.

(Compound (PA) Having Proton-Accepting Functional Group, Capable ofDecomposing Upon Irradiation with Actinic Rays or Radiation to GenerateProton-Accepting Compound which Exhibits Deterioration inProton-Accepting Properties, No Proton-Accepting Properties, or Changefrom Proton-Accepting Properties to Acidic Properties)

The composition according to the present invention may further include,as a basic compound, a compound [hereinafter also referred to as a“compound (PA)”] having a proton-accepting functional group, capable ofdecomposing upon irradiation with actinic rays or radiation to generatea compound which exhibits deterioration in proton-accepting properties,no proton-accepting properties, or a change from the proton-acceptingproperties to acidic properties.

The proton-accepting functional group denotes a functional group havinga group or an electron which is capable of electrostatically interactingwith a proton, and is, for example, a functional group with amacrocyclic structure such as a cyclic polyether, or a functional groupwhich has a nitrogen atom having an unshared electron pair notcontributing to π-conjugation. Examples of the nitrogen atom having anunshared electron pair not contributing to π-conjugation include anitrogen atom having a partial structure represented by the followinggeneral formula.

Preferred examples of a partial structure of the proton-acceptingfunctional group include crown ether, azacrown ether, primary totertiary amines, pyridine, imidazole, and a pyrazine structure.

The compound (PA) decomposes to generate a compound exhibitingdeterioration in proton-accepting properties, no proton-acceptingproperties, or a change from the proton-accepting properties to acidicproperties upon irradiation with actinic rays or radiation. Here, protonaccepting properties deteriorating, disappearing, or changing to acidicproperties represents a change in proton accepting properties caused byadding a proton to the proton-accepting functional group, andspecifically represents that, in a case where a proton adduct isgenerated using the compound (PA) having a proton-accepting functionalgroup and a proton, an equilibrium constant in the equilibrium constantis reduced.

Specific examples of the compound (PA) include the following compounds.Further, specific examples of the compound (PA) include compoundsdescribed in paragraphs 0421 to 0428 of JP2014-41328A and paragraphs0108 to 0116 of JP2014-134686A, the content of which is incorporatedherein by reference.

The basic compounds may be used singly or in combination of two or morekinds thereof.

The amount of the basic compound used is usually 0.001 to 10% by massand preferably 0.01 to 5% by mass with respect to the solid content ofthe actinic ray-sensitive or radiation-sensitive resin composition.

It is preferable that a ratio (molar ratio; photoacid generator/basiccompound) of the photoacid generator used to the basic compound used inthe composition is 2.5 to 300. That is, the molar ratio is preferably2.5 or more from the viewpoints of sensitivity and resolution, and ispreferably 300 or less from the viewpoint of suppressing deteriorationin resolution caused by thickening of a resist pattern with the lapse oftime until a heating treatment after exposure. The molar ratio(photoacid generator/basic compound) is more preferably 5.0 to 200 andstill more preferably 7.0 to 150.

As the basic compound, for example, a compound (for example, an aminecompound, an amido group-containing compound, a urea compound, or anitrogen-containing heterocyclic compound) described in paragraphs 0140to 0144 of JP2013-11833A can be used.

(A′) Hydrophobic Resin

The actinic ray-sensitive or radiation-sensitive resin composition mayinclude a hydrophobic resin (A′), in addition to the resin (A).

It is preferable that the hydrophobic resin is designed to be localizedon a surface of a resist film. Unlike the surfactant, the hydrophobicresin does not necessarily have a hydrophilic group in a molecule anddoes not necessarily contribute to uniform mixing with a polar/non-polarmaterial.

Examples of an effect obtained by the addition of the hydrophobic resininclude an effect of suppressing a static/dynamic contact angle of aresist film surface with respect to water and an effect of suppressingout gas.

From the viewpoint of localization on the film surface layer, thehydrophobic resin includes preferably one or more kinds and morepreferably two or more kinds among “a fluorine atom”, “a silicon atom”,and “a CH₃ partial structure included in a side chain of the resin”. Inaddition, it is preferable that the hydrophobic resin includes ahydrocarbon group having 5 or more carbon atoms. These groups may bepresent at a main chain or a side chain of the resin.

In a case where the hydrophobic resin includes a fluorine atom and/or asilicon atom, the fluorine atom and/or the silicon atom in thehydrophobic resin may be present at a main chain or a side chain of theresin.

In a case where the hydrophobic resin includes a fluorine atom, it ispreferable that a partial structure having a fluorine atom is an alkylgroup having a fluorine atom, a cycloalkyl group having a fluorine atom,or an aryl group having a fluorine atom.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbonatoms, and more preferably having 1 to 4 carbon atoms) is a linear orbranched alkyl group in which at least one hydrogen atom is substitutedwith a fluorine atom and may further have a substituent other than afluorine atom.

The cycloalkyl group having a fluorine atom is a monocyclic orpolycyclic cycloalkyl group in which at least one hydrogen atom issubstituted with a fluorine atom and may further have a substituentother than a fluorine atom.

Examples of the aryl group having a fluorine atom include an aryl group,such as a phenyl group and a naphthyl group, in which at least onehydrogen atom is substituted with a fluorine atom. The aryl group havinga fluorine atom may further have a substituent other than a fluorineatom.

Examples of a repeating unit having a fluorine atom or a silicon atominclude the repeating units described in paragraph 0519 ofUS2012/0251948A1.

Moreover, it is preferable that the hydrophobic resin includes a CH₃partial structure in a side chain as described above.

Here, examples of the CH₃ partial structure included in a side chain ofthe hydrophobic resin include a CH₃ partial structure such as an ethylgroup or a propyl group.

On the other hand, a methyl group (for example, an α-methyl group of arepeating unit having a methacrylic acid structure) which is directlybonded to a main chain of the hydrophobic resin has little contributionto the surface localization of the hydrophobic resin caused by theeffect of the main chain, and thus is not included in examples of theCH₃ partial structure according to the present invention.

With regard to the hydrophobic resin, reference can be made to thedescriptions in paragraphs [0348] to [0415] of JP2014-010245A, thecontent of which is incorporated herein by reference.

As the hydrophobic resin, resins described in JP2011-248019A,JP2010-175859A, and JP2012-032544A can also be preferably used.

(F) Surfactant

The actinic ray-sensitive or radiation-sensitive resin composition mayfurther include a surfactant (F). By incorporation of the surfactant,particularly in a case where an exposure light source having awavelength of 250 nm or shorter, in particular, 220 nm or shorter isused, a pattern having adhesiveness and reduced development defects canbe formed with high sensitivity and resolution.

As the surfactant, a fluorine-based surfactant and/or a silicon-basedsurfactant is particularly preferably used.

Examples of the fluorine-based surfactant and/or the silicon-basedsurfactant include the surfactants described in paragraph [0276] ofUS2008/0248425A. In addition, F-TOP EF301 or EF303 (manufactured by ShinAkita Chemical Co., Ltd.); FLUORAD FC430, 431, or 4430 (manufactured bySumitomo 3M Ltd.); MEGAFACE F171, F173, F176, F189, F113, F110, F177,F120, or R₀₈ (manufactured by DIC Corporation); SURFLON S-382, SC101,102, 103, 104, 105, or 106 (manufactured by Asahi Glass Co., Ltd.);TROYSOL S-366 (manufactured by Troy Corporation); GF-300 or GF-150(manufactured by Toagosei Co., Ltd.); SURFLON S-393 (manufactured by AGCSeimi Chemical Co., Ltd.); F-TOP EF121, EF122A, EF122B, RF122C, EF125M,EF135M, EF351, EF352, EF801, EF802, or EF601 (manufactured by GemcoInc.); PF636, PF656, PF6320, or PF6520 (manufactured by OMNOVA Corp.);or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, or 222D(manufactured by Neos Co., Ltd.) may be used. Further, a PolysiloxanePolymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can alsobe used as the silicon-based surfactant.

In addition, in addition to the known surfactants as shown above, asurfactant may be synthesized using a fluoro aliphatic compoundmanufactured using a telomerization method (also referred to as atelomer method) or an oligomerization method (also referred to as anoligomer method). Specifically, a polymer including a fluoro aliphaticgroup derived from fluoro aliphatic compound may be used as thesurfactant. This fluoro aliphatic compound can be synthesized, forexample, using the method described in JP2002-90991A.

In addition, a surfactant other than the fluorine-based surfactantand/or the silicon-based surfactant described in paragraph [0280] ofUS2008/0248425A may be used.

These surfactants may be used singly or in combination of two or morekinds thereof.

In a case where the actinic ray-sensitive or radiation-sensitive resincomposition includes the surfactant, the content of the surfactant ispreferably 0% to 2% by mass, more preferably 0.0001% to 2% by mass, andstill more preferably 0.0005% to 1% by mass, with respect to the totalsolid content of the composition.

(G) Other Additives

The actinic ray-sensitive or radiation-sensitive resin composition mayfurther include a dissolution inhibiting compound, a dye, a plasticizer,a photosensitizer, a light absorber, and/or a compound for promotingsolubility in the developer (for example, a phenol compound having amolecular weight of 1,000 or less, or an aliphatic or alicyclic compoundhaving a carboxy group).

The actinic ray-sensitive or radiation-sensitive resin composition mayfurther include a dissolution inhibiting compound.

Here, the “dissolution inhibiting compound” is a compound having amolecular weight of 3,000 or less, which decomposes by the action of anacid such that the solubility in the organic developer decreases.

[Upper Layer Film (Topcoat Film)]

In the pattern forming method of the present invention, an upper layerfilm (topcoat film) may be formed on the upper layer of the resist film.

It is preferable that the upper layer film is not mixed with the resistfilm, and can be uniformly applied onto the upper layer of the resistfilm.

The upper layer film is not particularly limited, and upper layer filmsknown in the related art can be formed by the methods known in therelated art, and the upper layer film can be formed in accordance with,for example, the description in paragraphs 0072 to 0082 ofJP2014-059543A. As a material for forming the upper layer film, ahydrophobic resin or the like can also be used, in addition to thepolymers described in paragraph 0072 of JP2014-059543A. As thehydrophobic resin, for example, the above-mentioned hydrophobic resin(A′) can be used.

In a case where a developer containing an organic solvent is used in thedeveloping step, it is preferable that an upper layer film containing abasic compound as described in JP2013-61648A, for example, is formed onthe resist film. Specific examples of the basic compound which can beincluded in the upper layer film include the above-mentioned basiccompound (E).

Furthermore, the upper layer film preferably includes a compound atleast one of a group or bond selected from the group consisting of anether bond, a thioether bond, a hydroxyl group, a thiol group, acarbonyl bond, and an ester bond.

In addition, the upper layer film may include a photoacid generator. Asthe photoacid generator, the same ones as the photoacid generator (forexample, the above-mentioned photoacid generator (B)) which can beincluded in the actinic ray-sensitive or radiation-sensitive resincomposition can be used.

Hereinafter, a resin which is preferably used in the upper layer film(topcoat film) will be described.

<Resin>

It is preferable that the composition for forming an upper layer filmcontains a resin. The resin which can be contained in the compositionfor forming an upper layer film is not particularly limited, but thesame resin as the hydrophobic resin (for example, the above-mentionedhydrophobic resin (A′)) which can be included in the actinicray-sensitive or radiation-sensitive resin composition can be used.

With regard to the hydrophobic resin, reference can be made to thedescriptions in

to [0023] of JP2013-61647A ([0017] to [0023] of the correspondingUS2013/244438A), and [0016] to [0165] of JP2014-56194A, the contents ofwhich is incorporated herein by reference.

In the present invention, the composition for forming an upper layerfilm preferably includes a resin containing a repeating unit having anaromatic ring. By the incorporation of the repeating unit having anaromatic ring, particularly upon irradiation with electron beams or EUVexposure, secondary electron-generating efficiency, and acid-generatingefficiency from a compound capable of generating an acid by actinic raysor radiation increase, and thus effects of realizing high sensitivityand high resolution in the formation of a pattern can be expected.

The weight-average molecular weight of the resin is preferably 3,000 to100,000, more preferably 3,000 to 30,000, and still more preferably5,000 to 20,000. The blend amount of the resin in the composition forforming an upper layer film is preferably 50% to 99.9% by mass, morepreferably 60% to 99.0% by mass, still more preferably 70% to 99.7% bymass, and even still more preferably 80% to 99.5% by mass, in the totalsolid content.

In a case where a plurality of the compositions (topcoat compositions)for forming an upper layer film contain a plurality of resins, thecompositions preferably include at least one resin (XA) having afluorine atom and/or a silicon atom.

As for a preferred range of the content of the fluorine atom and thesilicon atom contained in the resin (XA), the content of the repeatingunit including a fluorine atom and/or a silicon atom is preferably 10%to 100% by mass, more preferably 10% to 99% by mole, and still morepreferably 20% to 80% by mole in the resin (XA).

Furthermore, it is more preferable that the composition for forming anupper layer film includes at least one kind of the resin (XA) havingfluorine atoms and/or silicon atoms, and a resin (XB) having a smallercontent of the fluorine atoms and/or the silicon atoms than that of theresin (XA). Thus, in the formation of the upper layer film, the resin(XA) is unevenly distributed on the surface of the upper layer film, andtherefore, it is possible to improve performance such as developingcharacteristics and immersion liquid tracking properties.

The content of the resin (XA) is preferably 0.01% to 30% by mass, morepreferably 0.1% to 10% by mass, still more preferably 0.1% to 8% bymass, and particularly preferably 0.1% to 5% by mass, with respect tothe total solid content included in the composition for forming an upperlayer film. The content of the resin (XB) is preferably 50.0% to 99.9%by mass, more preferably 60% to 99.9% by mass, still more preferably 70%to 99.9% by mass, and particularly preferably 80% to 99.9% by mass, withrespect to the total solid content included in the composition forforming an upper layer film.

An embodiment in which the resin (XB) does not substantially containfluorine atoms and silicon atoms is preferable, and in this case,specifically, the total content of the repeating unit having a fluorineatom and the repeating unit having a silicon atom is preferably 0% to20% by mole, more preferably 0% to 10% by mole, still more preferably 0%to 5% by mole, particularly preferably 0% to 3% by mole, and ideally 0%by mole, that is, containing neither a fluorine atom nor a silicon atom,with respect to all the repeating units in the resin (XB).

<Method for Preparing Composition (Topcoat Composition) for FormingUpper Layer Film>

The composition for forming an upper layer film is preferably preparedby dissolving the respective components in a solvent, and filtered usinga filter. The filter is preferably a polytetrafluoroethylene-,polyethylene- or nylon-made filter having a pore size of 0.1 μM or less,more preferably 0.05 μM or less, and still more preferably 0.03 μm orless. Further, a plurality of kinds of the filters may be connected inseries or in parallel, and used. In addition, the composition may befiltered in plural times, and a step of filtering plural times may be acirculatory filtration step. Incidentally, the composition may besubjected to a deaeration treatment before and after the filtrationusing a filter. It is preferable that the composition for forming anupper layer film does not include impurities such as metals. The contentof the metal components included in these materials is preferably 10 ppmor less, more preferably 5 ppm or less, and still more preferably 1 ppmor less, but the material not having substantially metal components(within a detection limit or less of a determination device) isparticularly preferable.

In the above-mentioned <Exposing Step>, in a case where the exposure isliquid immersion exposure, the upper layer film is arranged between theactinic ray-sensitive or radiation-sensitive film and the immersionliquid, and also functions as a layer which does not bring the actinicray-sensitive or radiation-sensitive film into direct contact with theimmersion liquid. In this case, preferred characteristics required forthe upper layer film (composition for forming an upper layer film) arecoating suitability onto the actinic ray-sensitive orradiation-sensitive film, radiation, transparency, particularly to lightat 193 nm, and poor solubility in an immersion liquid (preferablywater). Further, it is preferable that the upper layer film is not mixedwith the actinic ray-sensitive or radiation-sensitive film, and can beuniformly applied onto the surface of the actinic ray-sensitive orradiation-sensitive film.

Moreover, in order to uniformly apply the composition for forming anupper layer film onto the surface of the actinic ray-sensitive orradiation-sensitive film while not dissolving the actinic ray-sensitiveor radiation-sensitive film, it is preferable that the composition forforming an upper layer film contains a solvent in which the actinicray-sensitive or radiation-sensitive film is not dissolved. It is morepreferable to use a solvent of components other than a developer(organic developer) containing an organic solvent as the solvent inwhich the actinic ray-sensitive or radiation-sensitive film is notdissolved.

A method for applying the composition for forming an upper layer film isnot particularly limited, and a spin coating method, a spray method, aroll coating method, a dip method, and the like which are known in therelated art can be used.

The film thickness of the upper layer film is not particularly limited,but from the viewpoint of transparency to an exposure light source, thetopcoat with a thickness of usually 5 nm to 300 nm, preferably 10 nm to300 nm, more preferably 20 nm to 200 nm, and still more preferably 30 nmto 100 nm is formed.

After forming the upper layer film, the substrate is heated (PB), asdesired.

From the viewpoint of resolution, it is preferable that the refractiveindex of the upper layer film is close to that of the actinicray-sensitive or radiation-sensitive film.

The upper layer film is preferably insoluble in an immersion liquid, andmore preferably insoluble in water.

With regard to the receding contact angle of the upper layer film, thereceding contact angle (23° C.) of the immersion liquid with respect tothe upper layer film is preferably 50° to 100°, and more preferably 80°to 100°, from the viewpoint of immersion liquid tracking properties.

In the liquid immersion exposure, in a view that the immersion liquidneeds to move on a wafer following the movement of an exposure head thatis scanning the wafer at a high speed and forming an exposure pattern,the contact angle of the immersion liquid with respect to the actinicray-sensitive or radiation-sensitive film in a dynamic state isimportant, and in order to obtain better resist performance, it ispreferable that the immersion liquid has a receding contact angle in theabove range.

During the release of the upper layer film, an organic developer may beused, and another release agent may also be used. As the release agent,a solvent hardly permeating the actinic ray-sensitive orradiation-sensitive film is preferable. In a view that the release ofthe upper layer film can be carried out simultaneously with thedevelopment of the actinic ray-sensitive or radiation-sensitive film,the upper layer film is preferably releasable with an organic developer.The organic developer used for the release is not particularly limitedas long as it makes it possible to dissolve and remove a less exposedarea of the actinic ray-sensitive or radiation-sensitive film.

From the viewpoint of the release using an organic developer, thedissolution rate of the upper layer film in the organic developer ispreferably 1 to 300 nm/sec, and more preferably 10 to 100 nm/sec.

Here, the dissolution rate of an upper layer film in the organicdeveloper refers to a film thickness decreasing rate in a case where theupper layer film is exposed to a developer after film formation, and isa rate in a case where the upper layer film is immersed in butyl acetateat 23° C. in the present invention.

An effect of reducing development defects after developing an actinicray-sensitive or radiation-sensitive film is accomplished by setting thedissolution rate of an upper layer film in the organic developer to 1nm/sec or more, and preferably 10 nm/sec or more. Further, an effectthat the line edge roughness of a pattern after the development of theactinic ray-sensitive or radiation-sensitive film becomes better isaccomplished as an effect of reducing the exposure unevenness duringliquid immersion exposure by setting the dissolution rate to 300 nm/secor less, and preferably 100 nm/sec.

The upper layer film may also be removed using other known developers,for example, an aqueous alkali solution. Specific examples of the usableaqueous alkali solution include an aqueous tetramethylammonium hydroxidesolution.

[Allowable Content of Impurities]

It is preferable that various materials (for example, the treatmentliquid (for example, a developer or a rinsing liquid) of the presentinvention, a resist solvent, a composition for forming an antireflectionfilm, and a composition for forming an upper layer film) used in theactinic ray-sensitive or radiation-sensitive resin composition and thepattern forming method according to the present invention do not includeimpurities such as metal, a metal salt including halogen, an acid, analkali, a sulfur-containing compound, and a phosphorous-containingcompound. The content of the impurities included in these materials ispreferably 1 ppm or less, more preferably 1 ppb or less, still morepreferably 100 ppt or less, and particularly preferably 10 ppt or less,but the material not having substantially metal components (within adetection limit or less of a determination device) is the mostpreferable.

Examples of a method for removing impurities such as metals from thevarious materials include filtration using a filter. As for the filterpore diameter, the pore size is preferably 10 nm or less, morepreferably 5 nm or less, and still more preferably 3 nm or less. As forthe materials of a filter, a polytetrafluoroethylene-, polyethylene-, ornylon-made filter is preferable. The filter may be formed of a compositematerial formed by combining this material with an ion exchange medium.As the filter, a filter which has been washed with an organic solvent inadvance may be used. In the step of filtration using a filter, aplurality of kinds of filters may be connected in series or in parallel,and used. In a case of using a plurality of kinds of filters, acombination of filters having different pore diameters and/or materialsmay be used. In addition, various materials may be filtered pluraltimes, and a step of filtering plural times may be a circulatoryfiltration step.

Moreover, examples of the method for reducing the impurities such asmetals included in the various materials include a method of selectingraw materials having a low content of metals as raw materialsconstituting various materials, a method of subjecting raw materialsconstituting various materials to filtration using a filter, and amethod of carrying out distillation under the condition for suppressingthe contamination as much as possible by, for example, lining the insideof a device with TEFLON (registered trademark). The preferred conditionsfor filtration using a filter, which is carried out for raw materialsconstituting various materials, are the same as the above-describedconditions.

Impurities may be removed using an adsorbing material, besides thefiltration using a filter, or may be removed using a combination offiltration using a filter and an adsorbing material. As the adsorbingmaterial, known adsorbing materials can be used, and for example,inorganic adsorbing materials such as silica gel and zeolite, andorganic adsorbing materials such as activated carbon can be used.

[Housing Container of Treatment Liquid]

It is preferable that the treatment liquid of the present invention,such as the developer and the rinsing liquid, is stored in a housingcontainer for a treatment liquid for patterning a chemically amplifiedresist film, in which the housing container has a housing section. Forexample, it is preferable that the housing container is a housingcontainer for a treatment liquid for patterning a chemically amplifiedresist film in which an inner wall of the housing section in contactwith the treatment liquid is formed of a resin other than any of apolyethylene resin, a polypropylene resin, and apolyethylene-polypropylene resin, or is formed of a metal which has beensubjected to a rust-preventing/metal elution-preventing treatment. Inthe housing section of the housing container, a predetermined organicsolvent to be used as a treatment liquid for patterning a chemicallyamplified resist film is stored, and during the patterning of thechemically amplified resist film, this organic solvent which has beendischarged from the housing section can be used.

In a case where the housing container further includes a sealing sectionfor sealing the housing section, it is preferable that the sealingsection is formed of a resin other than a resin selected from the groupconsisting of a polyethylene resin, a polypropylene resin, and apolyethylene-polypropylene resin, or is formed of a metal which has beensubjected to a rust-preventing/metal elution-preventing treatment.

Here, the sealing section denotes a member capable of isolating thehousing section from outside air, and preferred examples thereof includea packing and an O-ring.

The resin other than a resin selected from the group consisting of apolyethylene resin, a polypropylene resin, and apolyethylene-polypropylene resin is preferably a perfluoro resin.

Examples of the perfluoro resin include a polytetrafluoroethylene resin(PTFE), a tetrafluoroethylene-perfluoroalkylvinyl ether copolymer resin(PFA), a tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP),a tetrafluoroethylene-ethylene copolymer resin (ETFE), achlorotrifluoroethylene-ethylene copolymer resin (ECTFE), apolyvinylidene resin (PVDF), a polychlorotrifluoroethylene copolymerresin (PCTFE), and a polyvinyl fluoride resin (PVF).

Particularly preferred examples of the perfluoro resin include atetrafluoroethylene resin, a tetrafluoroethylene-perfluoroalkylvinylether copolymer resin, and a tetrafluoroethylene-hexafluoropropylenecopolymer resin.

Examples of the metal in the metal which has been subjected to therust-preventing/metal elution-preventing treatment include carbon steel,alloy steel, nickel-chrome steel, nickel chrome molybdenum steel, chromesteel, chrome molybdenum steel, and manganese steel.

As the rust-preventing/metal elution-preventing treatment, a coatingtechnique is preferably applied.

The coating technique is largely divided into three kinds of coatingssuch as metal coating (various platings), inorganic coating (variouschemical conversion treatments, glass, concrete, ceramics, and the like)and organic coating (rust preventive oil, paint, rubber, and plastics).

Preferred examples of the coating technique include a surface treatmentusing a rust-preventing oil, a rust inhibitor, a corrosion inhibitor, achelate compound, a releasable plastic, or a lining agent.

Among those, various corrosion inhibitors such as chromate, nitrite,silicate, phosphate, carboxylic acids such as oleic acid, dimer acid,and naphthalenic acid, a carboxylic acid metallic soap, sulfonate, anamine salt, esters (a glycerin ester or a phosphate ester of a higherfatty acid), chelate compounds such as ethylenediaminetetraacetic acid,gluconic acid, nitrilotriacetic acid,hydroxyethylethylenediaminetriacetic acid, anddiethylenetriaminepentaacetic acid, and a fluorine resin lining arepreferable. The phosphate treatment and the fluorine resin lining areparticularly preferable.

Furthermore, a “pre-treatment” which is at a pre-stage for therust-preventing treatment is also preferably employed as a treatmentmethod which leads to extension of an anti-rust period through a coatingtreatment although not directly preventing rust, as compared with adirect coating treatment.

Specific suitable examples of such a pre-treatment include a treatmentfor removing various corrosive factors, such as chloride and sulfate,present on a metal surface through washing or polishing.

Specific examples of the housing container include the following ones.

-   -   FluoroPurePFA complex drum manufactured by Entegris Inc. (liquid        contact inner surface; PFA resin lining)    -   Steel-made drum can manufactured by JFE (liquid contact inner        surface; zinc phosphate-coated film)

Moreover, examples of the housing container include the housingcontainers described in paragraphs 0013 to 0030 of JP1999-021393A(JP-H11-021393A), and the housing containers described in paragraphs0012 to 0024 of JP1998-45961A (JP-H10-45961A).

An electrically conductive compound may be added to the treatment liquidof the present invention in order to prevent the failure of chemicalliquid pipes or various parts (filters, O-rings, tubes, and the like)associated with electrostatic charge and subsequently occurringelectrostatic discharge.

Incidentally, since the treatment liquid of the present inventioncontains a high-polarity organic solvent having a relative dielectricconstant of 6.0 or more, it has an effect of suppressing the charging ofan antistatic device as it is, but can further suppress the charging ofan antistatic device by being used in combination with theabove-mentioned electrically conductive compound.

The electrically conductive compound is not particularly limited, butexamples thereof include methanol. The addition amount thereof is notparticularly limited, but is preferably 10% by mass or less, and morepreferably 5% by mass or less, from the viewpoint of maintainingpreferred development characteristics. For the members of the chemicalliquid pipes, various pipes coated with SUS or with polyethylene,polypropylene, or fluorine resins (polytetrafluoroethylene, aperfluoroalkoxy resin, and the like) which have been subjected to anantistatic treatment can be used. Similarly, with respect to the filtersand the O-rings, polyethylene, polypropylene, or fluorine resins(polytetrafluoroethylene, a perfluoroalkoxy resin, and the like) whichhave been subjected to an antistatic treatment can also be used.

EXAMPLES

Hereinafter, the present invention will be described in more detailusing examples, but the present invention is not limited to thefollowing Examples as long as it does not depart from the scope of thepresent invention. Unless otherwise specified, “parts” and “%” are givenon the basis of mass.

Furthermore, quantitative determination of metal salts including alkalior halogen in the treatment liquid (the treatment liquid described inTable 8) used in the development or rinsing in the following paragraphswere carried out, and as a result, it could be found that the treatmentliquid did not substantially include metal salts including alkali orhalogen.

Incidentally, similarly, for the treatment liquid (the treatment liquiddescribed in Table 8) used in the development or rinsing in thefollowing paragraphs, quantitative analysis of sulfur-containingcompounds (measured by, for example, the method specified in JIS K2541-6:2013 “Determination of sulfur content (Ultraviolet fluorescencemethod)”) and quantitative analysis of phosphorous compounds (measuredby spectrophotometry in terms of a total of phosphorous, based on themethod specified in JIS K 0102:2013), and as a result, it could beconfirmed that these compounds had not been substantially included.

In addition, the expression “doing not substantially having” hereinmeans that none is detected in a case where the content (concentration)of these compounds is measured by a measurable method (less than adetection limit value).

1. Preparation of Resist Composition and Composition for Forming UpperLayer Film

Hereinafter, various components used for the resist composition and thecomposition for forming an upper layer film, to be treated with thetreatment methods of Examples and Comparative Examples, and methods forpreparing the same will be described.

<Resin (A) and the Like>

(Synthesis Example 1) Synthesis of Resin (A-1)

600 g of cyclohexanone was put into a 2-L flask, and purged withnitrogen for 1 hour at a flow rate of 100 mL/min. Thereafter, 4.60 g(0.02 mol) of a polymerization initiator V-601 (manufactured by WakoPure Chemical Industries, Ltd.) was added thereto, and the flask waswarmed until the internal temperature reached 80° C. Next, the followingmonomers and 4.60 g (0.02 mol) of the polymerization initiator V-601(manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in200 g of cyclohexanone to prepare a monomer solution. The monomersolution was added dropwise to the flask which had been heated to 80° C.for 6 hours. After completion of the dropwise addition, the obtainedsolution was further reacted at 80° C. for 2 hours.

4-Acetoxystyrene: 48.66 g (0.3 mol)

1-Ethylcyclopentyl methacrylate: 109.4 g (0.6 mol)

Monomer 1: 22.2 g (0.1 mol)

The reaction solution was cooled to room temperature and added dropwiseto 3 L of hexane to precipitate a polymer. A solid obtained byfiltration was dissolved in 500 mL of acetone, added dropwise again to 3L of hexane, and then a solid obtained by filtration was dried underreduced pressure to obtain 160 g of a4-acetoxystyrene/1-ethylcyclopentyl methacrylate/monomer 1 copolymer(A-1a).

10 g of the polymer thus obtained, 40 mL of methanol, 200 mL of1-methoxy-2-propanol, and 1.5 mL of concentrated hydrochloric acid wereadded to a reaction vessel, heated to 80° C., and stirred for 5 hours.The reaction solution was left to be cooled to room temperature andadded dropwise to 3 L of distilled water. A solid obtained by filtrationwas dissolved in 200 mL of acetone, the solution was added dropwiseagain to 3 L of distilled water, and then, a solid obtained byfiltration was dried under reduced pressure to obtain a resin (A-1) (8.5g). As measured by gel permeation chromatography (GPC) (solvent:tetrahydrofuran (THF)) in terms of standard polystyrene, theweight-average molecular weight (Mw) was 11,200 and the molecular weightdispersity (Mw/Mn) was 1.45.

Resins (A-2) to (A-19), and (A-21) to (A-27) having the structures shownin Table 3 were synthesized by the same method as in Synthesis Example1, except that the monomers to be used were changed.

In Table 3, the compositional ratio (molar ratio) of the resin wascalculated by ¹H-NMR (nuclear magnetic resonance) measurement. Theweight-average molecular weight (Mw: in terms of polystyrene) and thedispersity (Mw/Mn) of the resin were calculated by GPC (solvent: THF)measurement. In addition, the weight-average molecular weights and thedispersities of the other resins shown in Examples were measured by thesame method.

TABLE 3 Compositional Ratio (molar ratio), From left Table 3-1 Structureside Mw Mw/Mn Resin A-1

30/60/10 11,200 1.45 Resin A-2

30/60/10 12,300 1.51 Resin A-3

40/20/40  9,200 1.68 Resin A-4

30/60/10 12,300 1.51 Resin A-5

20/80 12,500 1.52 Resin A-6

50/50 13,000 1.56 Resin A-7

70/30 12,500 1.43

TABLE 4 Composi - tional Ratio (molar ratio), Table From left Mw/ 3-2Structure side Mw Mn Resin A-8

20/80 18,000 1.12 Resin A-9

5/15/30/50 11,000 1.56 Resin A-10

50/50 11,000 1.45 Resin A-11

35/65 12,300 1.51 Resin A-12

60/40 12,500 1.68 Resin A-13

70/30 13,000 1.51 Resin A-14

20/40/40 11,000 1.45 Resin A-15

30/70 12,300 1.51

TABLE 5 Compositional Ratio (molar ratio), From left Table 3-3 Structureside Mw Mw/Mn Resin A-16

50/20/30 14,500 1.68 Resin A-17

30/50/10/10 12,100 1.53 Resin A-18

50/35/15 11,100 1.61 Resin A-19

30/45/15/10 11,500 1.49

TABLE 6 Compositional Ratio (molar Table ratio), From left 3-4 Structureside Mw Mw/Mn Product name Resin A-21

50/50 57,000 1.8 ZEP520A (manufactured by Nippon Zeon Co. Ltd., positivetone) Resin A-22

60/40 — — TEBN-1 (manufactured by Tokuyama Corp., negative tone) ResinHfO₂ + MAA — — — Hf nanoparticles (synthesized A-23 in accordance with“Solid- Solution Nanoparticles: Use of Nonhydrolytic Sol-Gel Synthesisto Prepare HfO₂ and Hf_(x)Zr_(1-x)O₂ Nanocrystals”, Tang, et al., Chem.Mater., 16, 1336 (2004), metal resist

TABLE 7 Compositional Ratio (molar ratio), From left Table 3-5 Structureside Mw Mw/Mn Resin A- 24

50/50 12,000 1.45 Resin A- 25

50/50 12,400 1.51 Resin A- 26

80/20 11,000 1.55 Resin A- 27

70/20/10 22,000 1.51

<Hydrophobic Resin (A′)>

As the hydrophobic resin, the following ones were used.

TABLE 8 Compositional ratio Table 4 (molar ratio) Mw Mw/Mn Resin (1b) 5045 5 — 7,000 1.30 Resin (2b) 40 40 20 — 18,600 1.57 Resin (3b) 50 50 — —25,400 1.63 Resin (4b) 30 65 5 — 28,000 1.70 Resin (5b) 10 10 30 5012,500 1.65

Specific structural formulae of the resins (1b) to (5b) described in thetable are shown below.

<Photoacid Generator (B)>

As the photoacid generator, the following ones were used.

<Basic Compound (E)>

As the basic compound, the following ones were used.

<Solvent (C)>

As the resist solvent, the following ones were used.

C-1: Propylene glycol monomethyl ether acetate

C-2: Propylene glycol monomethyl ether

C-3: Ethyl lactate

C-4: Cyclohexanone

C-5: Anisole

<Resist Composition>

The respective components shown in Table 5 below were dissolved in asolvent shown in the same table. The solution was filtered through apolyethylene filter having a pore size of 0.03 μm to obtain a resistcomposition.

TABLE 5 Acid Basic Hydro- Resin generator compound phobic (A) (B) (E)Solvent (C) resin (A’) Resist A-1 B-1 E-3 C-1 C-3 — — composition 1 0.77g 0.2 g 0.03 g 67.5 g 7.5 g — — Resist A-2 B-2 E-1 C-1 C-2 — —composition 2 0.79 g 0.18 g 0.03 g 45 g 30 g — — Resist A-3 B-2 E-1 C-1C-2 — — composition 3 0.79 g 0.18 g 0.03 g 45 g 30 g — — Resist A-4 B-2E-1 C-1 C-3 — — composition 4 0.79 g 0.18 g 0.03 g 60 g 15 g — — ResistA-5 B-3 E-3 C-1 C-3 — — composition 5 0.78 g 0.19 g 0.03 g 67.5 g 7.5 g— — Resist A-6 B-2 E-1 C-1 C-3 — — composition 6 0.79 g 0.18 g 0.03 g67.5 g 7.5 g — — Resist A-6/A-7 B-4 E-4 C-1 C-4 — — composition 7 0.395g/0.395 g 0.2 g 0.01 g 45 g 30 g — — Resist A-8 B-1 E-1 C-1 C-2 — —composition 8 0.79 g 0.18 g 0.03 g 45 g 30 g — — Resist A-1/A-2 B-2E-1/E-5 C-1 C-2 — — composition 9 0.395 g/0.395 g 0.18 g 0.015 g/0.015 g45 g 30 g — — Resist A-2 B-2 E-6 C-1 C-2 — — composition 10 0.79 g 0.18g 0.03 g 45 g 30 g — — Resist A-2 B-2 E-7 C-1 C-2 — — composition 110.79 g 0.18 g 0.03 g 45 g 30 g — — Resist A-2 B-2 E-8 C-1 C-2 — —composition 12 0.79 g 0.18 g 0.03 g 45 g 30 g — — Resist A-9 B-5 E-9 C-1C-2 C-4 5b composition 13 0.76 g 0.18 g 0.03 g 45 g 15 g 15 g 0.03 gResist A-7 B-5 E-9 C-1 C-2 C-4 4b composition 14 0.787 g 0.18 g 0.03 g45 g 15 g 15 g 0.003 g Resist A-6 B-4 E-10 C-1 C-2 C-4 3b composition 150.785 g 0.18 g 0.03 g 45 g 15 g 15 g 0.005 g Resist A-10 B-3 E-11 C-1C-2 C-4 2b composition 16 0.78 g 0.18 g 0.03 g 45 g 15 g 15 g 0.01 gResist A-11 B-6/B-2 E-12 C-1 C-2 C-4 1b composition 17 0.72 g 0.15g/0.09 g 0.03 g 45 g 15 g 15 g 0.01 g Resist A-12 B-7 E-13 C-1 C-2 — 5bcomposition 18 0.76 g 0.18 g 0.03 g 45 g 30 g — 0.03 g Resist A-13 B-8E-14 C-1 C-2 — 4b composition 19 0.787 g 0.18 g 0.03 g 30 g 45 g — 0.003g Resist A-14 B-9 E-2 C-1 C-4 — 3b composition 20 0.785 g 0.18 g 0.03 g45 g 30 g — 0.005 g Resist A-15 B-10/B-2 E-13 C-1 C-4 — 2b composition21 0.78 g 0.09 g/0.09 g 0.03 g 30 g 45 g — 0.01 g Resist A-16 B-6 E-14C-1 C-2 — 1b composition 22 0.71 g 0.25 g 0.03 g 50 g 10 g — 0.01 gResist A-17 B-2 E-1 C-1 C-3 — — composition 23 0.79 g 0.18 g 0.03 g 60 g15 g — — Resist A-18 B-2 E-1 C-1 C-3 — — composition 24 0.79 g 0.18 g0.03 g 60 g 15 g — — Resist A-19 B-2 E-1 C-1 C-3 — — composition 25 0.79g 0.18 g 0.03 g 60 g 15 g — — Resist A-24 B-11 E-14 C-1 C-2 — —composition 26 0.72 g 0.25 g 0.03 g 50 g 10 g — — Resist A-25 B-11 E-14C-1 C-2 — — composition 27 0.79 g 0.18 g 0.03 g 60 g 15 g — — ResistA-26 B-11 E-14 C-1 C-2 — — composition 28 0.79 g 0.18 g 0.03 g 60 g 15 g— — Resist A-27 B-11 E-14 C-1 C-2 — — composition 29 0.79 g 0.18 g 0.03g 60 g 15 g — — Acid Basic Resin generator compound Solvent Other (A)(B) (E) (C) additive Resist A-21 — — C-5 — composition 31 1 g — — 75 g —Resist A-22 — — C-1 — composition 32 1 g — — 75 g — Resist A-23 B-4 —C-1 — composition 33 0.95 g 0.05 g — 75 g —

<Composition for Forming Upper Layer Film>

The respective components shown in Table 6 below were dissolved in asolvent shown in the same table. The solution was filtered through apolyethylene filter having a pore size of 0.03 μm to obtain acomposition for forming an upper layer film. Incidentally, “MIBC” in thefollowing table represents methyl isobutyl carbinol.

TABLE 6 Composition for forming Solvent upper Photoacid (mixing ratiolayer film Resin generator Additive (mass ratio)) T-1 V1 — — MIBC/decane1.0 g — — 30/70 T-2 V1 B-2 — MIBC/decane 1.0 g 0.02 g — 50/50 T-3 V1 —E-11 MIBC/decane 1.0 g — 0.02 g 30/70 T-4 V1 — X1 MIBC/decane 1.0 g —0.02 g 30/70 T-5 V1 B-2 X1 MIBC/decane 1.0 g 0.02 g 0.02 g 30/70 T-6 V2— — MIBC/decane 1.0 g — — 30/70 T-7 V3 — — MIBC/decane 1.0 g — — 30/70T-8 V4 — — MIBC/decane 1.0 g — — 30/70 T-9 V1:1b — — MIBC/undecane 0.9g:0.1 g — — 20/80

Resins V-1 to V-4, and 1b, and an additive X1 which were used are shownbelow. The other additives are the same as described above.

The compositional ratios, the weight-average molecular weights, and thedispersities of the resins V-1 to V-4, and 1b are shown in another table(Table 7).

TABLE 7 Resin for Compositional Weight-average forming upper ratiomolecular layer film (molar ratio) weight Dispersity V-1 40/40/20 11,0001.45 V-2 60/40 9,500 1.59 V-3 40/40/20 9,300 1.67 V-4 30/70 12,000 1.331b 40/50/10 11,000 1.45

2. EUV Exposure (Examples 1-1 to 1-44, and Comparative Examples 1-1 to1-7)

<EUV Exposure Evaluation>

Using the resist composition described in Table 5, a resist pattern wasformed through the following operation.

[Application and Post-Application Baking (PB) of Resist Composition]

An organic film DUV44 (manufactured by Brewer Science, Inc.) was appliedonto a 12-inch silicon wafer (1 inch=2.54 cm), and baked at 200° C. for60 seconds to form an organic film having a film thickness of 60 nm.Each of the resist compositions obtained as above was applied thereontoand baked for 60 seconds under the conditions of 90° C. to 180° C.(refer to the PB section in Table 9) to form a resist film having a filmthickness of 40 nm.

Incidentally, the resist composition 31 used in Example 1-25 was apositive tone resist composition, and in the other Examples andComparative Examples, negative tone resist compositions were used.

[Application and Post-Application Baking (PB) of Composition for FormingUpper Layer Film]

With regard to Examples 1-30 to 1-37, and 1-42 to 1-44, the composition(topcoat composition) for forming an upper layer film shown in Table 6was applied onto the baked resist film, and then baked at a PBtemperature (unit: ° C.) shown in Table 9 over 60 seconds to form anupper layer film (topcoat) having a film thickness of 40 nm.

[Exposure]

(L/S Pattern)

The wafer manufactured above was subjected to EUV exposure with anumerical aperture (NA) of 0.25 and a dipole illumination (Dipole 60x,outer sigma of 0.81, inner sigma of 0.43). Specifically, the EUVexposure was carried out by varying the exposure doses through a maskincluding a pattern (for evaluation of pattern collapse of L/S) forforming a line-and-space pattern in a dimension with a pitch of 40 nmand a width of 20 nm on the wafer.

(C/H Pattern)

The wafer manufactured above was subjected to EUV exposure with anumerical aperture (NA) of 0.25 and a Quasar illumination (Quasar 45,outer sigma of 0.81, inner sigma of 0.51). Specifically, the EUVexposure was carried out by varying the exposure doses through a maskincluding a pattern (for evaluation of pattern collapse of C/H) forforming a contact hole pattern in a dimension with a pitch of 60 nm anda hole size of 30 nm on the wafer.

[Post-Exposure Baking (PEB)]

After the irradiation, the film was taken out from the EUV exposuredevice, and immediately baked for 60 seconds under the conditions of 85°C. to 130° C. (refer to the PEB section in Table 9).

[Development]

Thereafter, using a shower type developing device (ADE3000S,manufactured by ACTES Kyosan, Inc.), development was carried out byspray-discharging a developer (23° C.) for 30 seconds at a flow rate of200 mL/min while rotating the wafer at 50 rotations (rpm). Further, asthe developer, any one treatment liquid out of S-1 to S-20, and SA-1 toSA-9 described in Table 8 was used. The types of the developers used inthe respective Examples and Comparative Examples are shown in Table 9.

TABLE 13 Other organic solvents or First organic solvent Second organicsolvent Mixing ratio components to be added Mixing ratio Treat- RelativeRelative (first:second = Organic solvents Relative (first:second:others= ment Organic dielectric Organic dielectric % by weight:% or componentsto dielectric % by weight:% by liquid solvent constant solvent constantby weight) be added constant weight:% by weight) S-1 Undecane 2.0 PGME12.3 80:20 — — — S-2 Decane 2.0 Cyclo- 18.2 80:20 — — — hexanone S-3Octane 2.0 2-heptanone 12.0 80:20 — — — (MAK) S-4 Dodecane 2.05-nonanone 10.6 80:20 — — — S-5 Dipropyl ether 3.4 PGMEA 8.3 80:20 — — —S-6 Di-isopropyl 4.0 Ethyl lactate 13.1 80:20 — — — ether S-7 Undecane2.0 3.3-dimethyl- 13.1 80:20 — — — 2-butanone S-8 Undecane 2.04-heptanone 12.6 80:20 — — — S-9 Undecane 2.0 Di-isobutyl 9.9 90:10 — —— ketone S-10 Undecane 2.0 Di-isobutyl 9.9 70:30 — — — ketone S-11Undecane 2.0 Di-isobutyl 9.9 60:40 — — — ketone S-12 Undecane 2.0Di-isobutyl 9.9 40:60 — — — ketone S-13 Undecane 2.0 Di-isobutyl 9.9 —2-methyl 2- 23.7 (as second 80:10:10 ketone nitropropane organicsolvent) S-14 Undecane 2.0 Di-isobutyl 9.9 — 5-nonanone 10.6 (as second80:10:10 ketone organic solvent) S-15 Undecane 2.0 Di-isobutyl 9.9 —Decane 2.0 (as first 60:20:20 ketone organic solvent) S-16 Dipropylether 3.4 PGME 12.3 — IL-P14 (manu- 17:80:3 factured by Koei ChemicalCo., Ltd.) S-17 Undecane 2.0 Di-isobutyl 9.9 10:90 — — — ketone S-18Undecane 2.0 Di-isobutyl 9.9 20:80 — — — ketone S-19 Undecane 2.0 PGME12.3 20:80 — — — S-20 Undecane 2.0 Di-isobutyl 9.9 30:70 — — — ketoneSA-1 2,6-dimethyl 4- 9.9 2-heptanone 12.0 50:50 — — — heptanone (MAK)SA-2 2,6-dimethyl 4- 9.9 2-heptanone 12.0 25:75 — — — heptanone (MAK)SA-3 2,6-dimethyl 4- 9.9 2-heptanone 12.0 75:25 — — — heptanone (MAK)SA-4 2,6-dimethyl 4- 9.9 2-heptanone 12.0 80:20 — — — heptanone (MAK)SA-5 n-butyl acetate 5.0 n-hexyl 4.4 80:20 — — — acetate SA-6Di-n-propyl 3.4 Di-isopropyl 4 80:20 — — — ether ether SA-7 Isoamylacetate 4.8 — — — — — — SA-8 n-butyl acetate 5.0 — — — — — — SA-9Dodecane 2.0 — — — — — —

Here, in Table 8, the relative dielectric constant of eachdeveloper/rinsing liquid is a value using the relative dielectricconstant (usually the value at a temperature of 20° C.) described in“Handbook of Organic Solvent Properties, Ian M. Smallwood, 1996,Elsevier” and “CRC Handbook of Chemistry and Physics, 96th Edition,William M. Haynes, 2015, CRC Press”.

[Rinsing]

Thereafter, a rinsing treatment was carried out by spray-discharging arinsing liquid (23° C.) for 15 seconds at a flow rate of 200 mL/minwhile rotating the wafer at 50 rotations (rpm).

Lastly, the wafer was dried by high-speed rotating it for 60 seconds at2,500 rotations (rpm). Further, as the rinsing liquid, any one treatmentliquid out of S-1 to S-20, and SA-1 to SA-9 described in Table 8 wasused. The types of the rinsing liquids used in the respective Examplesand Comparative Examples are shown in Table 9.

[Evaluation Test]

With regard to the following items, evaluation of the resist pattern wascarried out. Details of the results are shown in Table 9.

(Pattern Collapse Performance of L/S)

The resolution states of the line-and-space patterns exposed atdifferent exposure doses were observed at a magnification of 200 k,using a scanning electron microscope (S-9380II, manufactured by Hitachi,Ltd.), and a minimum line width with which the pattern collapse did notoccur in one field of view observed was determined and used as an indexof the pattern collapse. A smaller numeral value thereof indicatesbetter pattern collapse performance.

(Omission Performance of C/H)

The resolution states of the contact hole patterns exposed at differentexposure doses were observed at a magnification of 200 k, using ascanning electron microscope (S-9380II, manufactured by Hitachi, Ltd.),and a minimum hole size with which the omission failure of a hole didnot occur in one field of view observed was determined and used as anindex of the omission performance of C/H. A smaller numeral valuethereof indicates better omission performance of C/H.

TABLE 14 PB Upper PB of upper PEB L/S C/H (60 layer layer film (60collapse omission Table 9 seconds) film (60 seconds) seconds)Development Rinsing (nm) (nm) Example 1-1 Resist composition 9  90° C. —— 110° C. SA-8 S-1 13.2 27.5 Example 1-2 Resist composition 8 100° C. —— 110° C. SA-8 S-2 14.1 28.7 Example 1-3 Resist composition 7 110° C. —— 100° C. SA-7 S-3 13.1 24.2 Example 1-4 Resist composition 6 120° C. —— 120° C. SA-8 S-4 18.0 23.8 Example 1-5 Resist composition 4  90° C. ——  85° C. SA-8 S-5 15.4 25.2 Example 1-6 Resist composition 5 130° C. —— 110° C. SA-8 S-6 17.0 26.9 Example 1-7 Resist composition 3 100° C. —— 110° C. SA-7 S-7 14.5 20.1 Example 1-8 Resist composition 2 110° C. —— 110° C. SA-7 S-8 13.2 23.8 Example 1-9 Resist composition 1 120° C. ——  90° C. SA-7 S-9 14.8 21.5 Example 1-10 Resist composition 7 110° C. —— 100° C. SA-7 S-10 14.1 20.1 Example 1-11 Resist composition 13 100° C.— — 110° C. SA-7 S-11 13.9 22.1 Example 1-12 Resist composition 11 120°C. — — 130° C. SA-7 S-12 15.4 20.5 Example 1-13 Resist composition 12110° C. — — 110° C. SA-7 S-13 14.5 21.1 Example 1-14 Resist composition9  90° C. — — 110° C. SA-7 S-14 14.8 22.3 Example 1-15 Resistcomposition 8 100° C. — — 110° C. SA-7 S-15 14.3 21.4 Example 1-16Resist composition 7 110° C. — — 100° C. SA-7 S-16 13.3 23.0 Example1-17 Resist composition 6 120° C. — — 120° C. SA-7 S-11 14.6 21.6Example 1-18 Resist composition 4  90° C. — —  85° C. S-17 S-12 14.821.1 Example 1-19 Resist composition 5 130° C. — — 110° C. S-18 S-1313.3 22.8 Example 1-20 Resist composition 3 100° C. — — 110° C. S-19S-14 13.0 22.3 Example 1-21 Resist composition 2 110° C. — — 110° C.S-17 SA-9 13.6 26.2 Example 1-22 Resist composition 1 120° C. — —  90°C. S-18 SA-9 14.7 27.8 Example 1-23 Resist composition 12 110° C. — —110° C. S-19 SA-9 14.0 26.2 Example 1-24 Resist composition 33 — — — —SA-8 S-4 17.0 23.2 Example 1-25 Resist composition 31 180° C. — — — SA-85-5 15.7 23.2 Example 1-26 Resist composition 32 110° C. — — — SA-8 S-616.6 28.8 Example 1-27 Resist composition 3 120° C. — —  85° C. SA-7S-17 14.8 22.9 Example 1-28 Resist composition 4 110° C. — —  90° C.SA-7 S-18 13.9 22.5 Example 1-29 Resist composition 5 100° C. — — 110°C. SA-7 S-20 13.1 22.5 Example 1-30 Resist composition 4 120° C. T-1 90° C.  90° C. SA-7 S-11 14.8 20.3 Example 1-31 Resist composition 4120° C. T-2 120° C.  90° C. SA-7 S-11 13.2 22.5 Example 1-32 Resistcomposition 4 120° C. T-3  90° C.  90° C. SA-7 S-11 14.7 20.0 Example1-33 Resist composition 4 120° C. T-4 120° C.  90° C. SA-7 5-11 13.220.3 Example 1-34 Resist composition 4 120° C. T-5 120° C.  90° C. SA-75-11 14.3 20.8 Example 1-35 Resist composition 4 120° C. T-6  90° C. 90° C. SA-7 S-1l 13.8 22.1 Example 1-36 Resist composition 4 120° C.T-7 120° C.  90° C. SA-7 S-11 14.8 20.0 Example 1-37 Resist composition4 120° C. T-8  90° C.  90° C. SA-7 S-11 13.7 20.3 Example 1-38 Resistcomposition 4 120° C. — —  85° C. SA-7 S-20 14.3 22.5 Example 1-39Resist composition 23 120° C. — —  90° C. SA-1 S-20 14.4 22.5 Example1-40 Resist composition 24 120° C. — — 110° C. SA-1 S-20 14.4 22.6Example 1-41 Resist composition 25 120° C. — —  95° C. SA-1 S-20 14.422.5 Example 1-42 Resist composition 25 120° C. T-1  90° C.  95° C. SA-1S-20 14.5 22.4 Example 1-43 Resist composition 4 120° C. T-9 120° C. 90° C. SA-7 S-10 14.2 20.5 Example 1-44 Resist composition 25 120° C.T-9  90° C.  90° C. SA-1 S-20 14.1 22.5 Comparative Resist composition 7 90° C. — — 120° C. SA-8 SA-9 20.2 42.1 Example 1-1 Comparative Resistcomposition 7  90° C. — — 120° C. SA-8 SA-3 21.8 29.9 Example 1-2Comparative Resist composition 7  90° C. — — 120° C. SA-8 SA-4 20.7 30.5Example 1-3 Comparative Resist composition 7  90° C. — — 120° C. SA-8SA-6 21.2 38.6 Example 1-4 Comparative Resist composition 7  90° C. — —120° C. SA-1 SA-6 21.7 44.5 Example 1-5 Comparative Resist composition 7 90° C. — — 120° C. SA-2 SA-9 20.1 33.8 Example 1-6 Comparative Resistcomposition 7  90° C. — — 120° C. SA-5 SA-9 20.0 43.1 Example 1-7

3. EUV Exposure-Double Patterning (Example 1-45)

[Application and Post-Application Baking (PB) of Resist Composition]

An organic film DUV44 (manufactured by Brewer Science, Inc.) was appliedonto a 12-inch silicon wafer, and baked at 200° C. for 60 seconds toform an organic film having a film thickness of 60 nm. The resistcomposition 1 was applied thereonto and baked for 60 seconds at 90° C.to form a resist film having a film thickness of 60 nm.

[Exposure]

(L/S Pattern)

The wafer manufactured above was subjected to EUV exposure with anumerical aperture (NA) of 0.25 and a dipole illumination (Dipole 60x,outer sigma of 0.81, inner sigma of 0.43). Specifically, a first EUVexposure was carried out through a mask including a pattern with a spaceof 40 nm and a line pattern of 120 nm, and a second exposure was carriedout with the same pattern as the first mask while the position of a maskwas shifted 80 nm to arrange a space between the first exposure spaces.

(C/H Pattern)

The wafer manufactured above was subjected to a first EUV exposure witha numerical aperture (NA) of 0.25 and a Dipole illumination (Xdeflection, Dipole 60x, outer sigma of 0.81, inner sigma of 0.43), usinga line-space mask with a half pitch of 30 nm, and then to a second EUVexposure with a Dipole illumination (Y deflection, Dipole 60y, outersigma of 0.81, inner sigma of 0.43), using a line-space mask with a halfpitch of 30 nm.

[Development]

Thereafter, using a shower type developing device (ADE3000S,manufactured by ACTES Kyosan, Inc.), development was carried out byusing a treatment liquid SA-7 shown in Table 8 as a developer (23° C.)while rotating the wafer at 50 rotations (rpm), and spray-discharging itfor 30 seconds at a flow rate of 200 mL/min.

[Rinsing]

Thereafter, a rinsing treatment was carried out by using a treatmentliquid S-11 shown in Table 8 as a rinsing liquid (23° C.) while rotatingthe wafer at 50 rotations (rpm), and spray-discharging it for 15 secondsat a flow rate of 200 mL/min. Lastly, the wafer was dried by high-speedrotating it for 60 seconds at 2,500 rotations (rpm).

[Evaluation Test]

(Results of L/S Pattern Evaluation) The exposure was carried out whileappropriately adjusting the exposure dose for forming a pattern, and asa result, a pattern with a line of 14 nm and a pitch of 40 nm wasresolved without pattern collapse.

(Results of C/H Pattern Evaluation)

The exposure was carried out while appropriately adjusting the exposuredose for forming a pattern, and as a result, a pattern with a hole of 23nm and a pitch of 60 nm was resolved without omission failure of C/H.

4. EB Exposure (Examples 2-1 to 2-27, and Comparative Examples 2-1 to2-7)

<EB Exposure Evaluation>

Using the resist composition described in Table 5, a resist pattern wasformed through the following operation.

[Application and Post-Application Baking (PB) of Resist Composition]

An organic film DUV44 (manufactured by Brewer Science, Inc.) was appliedonto a 6-inch silicon wafer, and baked at 200° C. for 60 seconds to forman organic film having a film thickness of 60 nm. The resist compositiondescribed in Table 5 was applied thereonto and baked for 60 secondsunder the conditions of 90° C. to 180° C. (refer to the PB section inTable 10) to form a resist film having a film thickness of 40 nm.

Incidentally, the resist composition 31 used in Example 2-25 was apositive tone resist composition, and in the other Examples andComparative Examples, negative tone resist compositions were used.

[Exposure]

(L/S Pattern)

The wafer manufactured above was subjected to EB exposure (forevaluation of pattern collapse of L/S) by designing a layout of EBdrawing as in the formation of a line-and-space pattern having adimension on the wafer with a pitch of 40 nm and a width of 20 nm, andvarying the exposure doses, using an electron beam irradiation device(JBX6000FS/E, manufactured by JEOL; accelerating voltage of 50 keV).

(C/H Pattern)

The wafer manufactured above was subjected to EB exposure (forevaluation of pattern collapse of C/H) by designing a layout of EBdrawing for forming a contact hole pattern for the formation of acontact hole pattern having a dimension on the wafer with a pitch of 60nm and a hole size of 30 nm, and varying the exposure doses.

[Post-Exposure Baking (PEB)]

After the irradiation, the film was taken out from the electron beamirradiation device, and immediately heated on a hot plate under theconditions of 85° C. to 130° C. (refer to the PEB section in Table 10)for 60 seconds.

[Development]

Using a shower type developing device (ADE3000S, manufactured by ACTESKyosan, Inc.), development was carried out by spray-discharging adeveloper (23° C.) for 30 seconds at a flow rate of 200 mL/min whilerotating the wafer at 50 rotations (rpm). Further, as the developer, anyone treatment liquid out of S-1 to S-20 and SA-1 to SA-9 described inTable 8 was used. The types of the developers used in the respectiveExamples and Comparative Examples are shown in Table 10.

[Rinsing]

Thereafter, a rinsing treatment was carried out by spray-discharging arinsing liquid (23° C.) for 15 seconds at a flow rate of 200 mL/minwhile rotating the wafer at 50 rotations (rpm).

Lastly, the wafer was dried by high-speed rotating it for 60 seconds at2,500 rotations (rpm). Further, as the rinsing liquid, any one treatmentliquid out of S-1 to S-20 and SA-1 to SA-9 described in Table 8 wasused. The types of the rinsing liquids used in the respective Examplesand Comparative Examples are shown in Table 10.

[Evaluation Test]

With regard to the same items as in the above-mentioned “EUV ExposureEvaluation”, evaluation of the resist pattern was carried out by thesame method as above, except that “5-9220” (manufactured by Hitachi,Ltd.) was used as a scanning electron microscope. Details of the resultsare shown in Table 10.

TABLE 15 PB PEB L/S C/H (60 (60 collapse omission Table 10 seconds)seconds) Development Rinsing (nm) (nm) Example 2-1 Resist composition 9 90° C. 110° C. SA-8 S-1 13.1 27.8 Example 2-2 Resist composition 8 100°C. 110° C. SA-8 S-2 13.9 28.1 Example 2-3 Resist composition 7 110° C.100° C. SA-7 S-3 14.4 25.1 Example 2-4 Resist composition 6 120° C. 120°C. SA-8 S-4 17.9 24.8 Example 2-5 Resist composition 4  90° C.  85° C.SA-8 S-5 16.4 25.6 Example 2-6 Resist composition 5 130° C. 110° C. SA-8S-6 17.2 26.8 Example 2-7 Resist composition 3 100° C. 110° C. SA-7 S-714.7 21.0 Example 2-8 Resist composition 2 110° C. 110° C. SA-7 S-8 13.325.4 Example 2-9 Resist composition 1 120° C.  90° C. SA-7 S-9 14.7 22.7Example 2-10 Resist composition 7 110° C. 100° C. SA-7 S-10 14.3 22.3Example 2-11 Resist composition 13 100° C. 110° C. SA-7 S-11 14.3 20.2Example 2-12 Resist composition 11 120° C. 130° C. SA-7 S-12 14.8 20.8Example 2-13 Resist composition 12 110° C. 110° C. SA-7 S-13 13.8 22.4Example 2-14 Resist composition 9  90° C. 110° C. SA-7 S-14 14.4 22.5Example 2-15 Resist composition 8 100° C. 110° C. SA-7 S-15 14.8 20.1Example 2-16 Resist composition 7 110° C. 100° C. SA-7 S-16 14.4 20.2Example 2-17 Resist composition 6 120° C. 120° C. SA-7 S-11 14.1 20.6Example 2-18 Resist composition 4  90° C.  85° C. S-17 S-12 14.1 21.6Example 2-19 Resist composition 5 130° C. 110° C. S-18 S-13 14.1 20.3Example 2-20 Resist composition 3 100° C. 110° C. S-19 S-14 14.3 22.4Example 2-21 Resist composition 2 110° C. 110° C. S-17 SA-9 14.5 26.6Example 2-22 Resist composition 1 120° C.  90° C. S-18 SA-9 14.2 26.5Example 2-23 Resist composition 12 110° C. 110° C. S-19 SA-9 13.4 28.3Example 2-24 Resist composition 33 — — SA-8 S-4 16.6 25.7 Example 2-25Resist composition 31 180° C. — SA-8 5-5 15.1 26.0 Example 2-26 Resistcomposition 32 110° C. — SA-8 S-6 17.0 29.2 Example 2-27 Resistcomposition 25 110° C.  90° C. S-17 SA-9 14.3 20.9 Comparative Resistcomposition 7  90° C. 120° C. SA-8 SA-9 20.9 39.1 Example 2-1Comparative Resist composition 7  90° C. 120° C. SA-8 SA-3 21.6 30.7Example 2-2 Comparative Resist composition 7  90° C. 120° C. SA-8 SA-421.5 30.5 Example 2-3 Comparative Resist composition 7  90° C. 120° C.SA-8 SA-6 20.9 38.4 Example 2-4 Comparative Resist composition 7  90° C.120° C. SA-1 SA-6 20.2 40.5 Example 2-5 Comparative Resist composition 7 90° C. 120° C. SA-2 SA-9 20.8 42.3 Example 2-6 Comparative Resistcomposition 7  90° C. 120° C. SA-5 SA-9 20.0 43.5 Example 2-7

5. ArF Exposure (Examples 3-1 to 3-35, and Comparative Examples 3-1 to3-7)

<ArF Exposure Evaluation>

Using the resist composition described in Table 5, a resist pattern wasformed through the following operation.

[Application and Post-Application Baking (PB) of Resist Composition]

An organic antireflection film ARC29SR (manufactured by Brewer Science,Inc.) was applied onto a 8-inch silicon wafer, and baked at 205° C. for60 seconds to form an antireflection film having a film thickness of 86nm. Each of the resist compositions obtained as above was appliedthereonto and baked for 60 seconds under the conditions of 90° C. to120° C. (refer to the PB section in Table 11) to form a resist filmhaving a film thickness of 40 nm.

[Application and Post-Application Baking (PB) of Composition for FormingUpper Layer Film]

With regard to Examples 3-24 to 3-31 and 3-33 to 3-35, the composition(topcoat composition) for forming an upper layer film shown in Table 6was applied onto the baked resist film, and then baked at a PBtemperature (unit: ° C.) shown in Table 11 over 60 seconds to form anupper layer film (topcoat) having a film thickness of 40 nm.

[Exposure]

(L/S Pattern)

The wafer manufactured above was subjected to patternwise exposure ofthe resist film through a 6% halftone mask (with a space portionshielded) having a 1:1 line-and-space pattern with a line width of 50nm, using an ArF excimer liquid immersion scanner (manufactured by ASML;XT1700i, NA1.20, C-Quad, outer sigma of 0.750, inner sigma of 0.650, andY deflection) while varying the exposure doses. Ultrapure water was usedas an immersion liquid. Thereafter, the resist film was heated for 60seconds under the conditions of 90° C. to 120° C. (refer to the PEBsection in Table 11). Then, the resist film was developed by puddling itfor 30 seconds with a developer described in Table 11 (with regard toeach of the developers, refer to Table 8), using a development device(RF3; manufactured by SOKUDO Co., Ltd.). Thereafter, rinsing was carriedout for 15 seconds with a rinsing liquid described in Table 11 (withregard to each of the rinsing liquids, refer to Table 8) while rotatingthe wafer at 50 rotations (rpm), and subsequently, the wafer was rotatedfor 30 seconds at a rotation speed of 2,000 rpm to obtain aline-and-space pattern.

(C/H Pattern)

The wafer manufactured above was subjected to patternwise exposure ofthe resist film through a 6% halftone mask with 65 nm of a hole portionand a square array with a pitch between holes of 100 nm (with a spaceportion shielded), using an ArF excimer liquid immersion scanner(manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma of 0.730,inner sigma of 0.630, and XY deflection) while varying the exposuredoses. Ultrapure water was used as an immersion liquid. Thereafter, theresist film was heated for 60 seconds under the conditions of 90° C. to120° C. (refer to the PEB section in Table 11). Then, the resist filmwas developed by puddling it for 30 seconds with a developer describedin Table 11 (with regard to each of the developers, refer to Table 8),using a development device (RF³; manufactured by SOKUDO Co., Ltd.).Thereafter, rinsing was carried out for 15 seconds with a rinsing liquiddescribed in Table 11 (with regard to each of the rinsing liquids, referto Table 8) while rotating the wafer at 50 rotations (rpm), andsubsequently, the wafer was rotated for 30 seconds at a rotation speedof 2,000 rpm to obtain a hole pattern.

[Evaluation Test]

With regard to the same items as in the above-mentioned “EUV ExposureEvaluation”, evaluation of the resist pattern was carried out by thesame method as above, using “S-9380II” (manufactured by Hitachi, Ltd.)as a scanning electron microscope. Details of the results are shown inTable 11.

TABLE 16 PB Upper PB (60 PEB L/S C/H (60 layer seconds) of (60 collapseomission Table 11 seconds) film upper layer film seconds) DevelopmentRinsing (nm) (nm) Example 3-1 Resist composition 14 120° C. — — 120° C.SA-8 S-1 38.4 61.9 Example 3-2 Resist composition 15 110° C. — —  90° C.SA-8 S-2 36.7 62.7 Example 3-3 Resist composition 16 100° C. — — 120° C.SA-7 S-3 37.5 57.5 Example 3-4 Resist composition 17  90° C. — —  90° C.SA-8 S-4 47.0 56.9 Example 3-5 Resist composition 18 120° C. — — 120° C.SA-8 S-5 40.9 57.3 Example 3-6 Resist composition 19 110° C. — —  90° C.SA-8 S-6 46.1 64.3 Example 3-7 Resist composition 20 100° C. — — 120° C.SA-7 S-7 36.6 53.6 Example 3-8 Resist composition 21  90° C. — —  90° C.SA-7 S-8 38.5 57.5 Example 3-9 Resist composition 22 120° C. — — 120° C.SA-7 S-9 39.5 54.5 Example 3-10 Resist composition 14 110° C. — —  90°C. SA-7 S-10 38.5 55.4 Example 3-11 Resist composition 15 100° C. — —120° C. SA-7 S-11 38.7 53.8 Example 3-12 Resist composition 16  90° C. ——  90° C. SA-7 S-12 38.3 53.4 Example 3-13 Resist composition 17 120° C.— — 120° C. SA-7 S-13 36.7 53.1 Example 3-14 Resist composition 18 110°C. — —  90° C. SA-7 S-14 36.4 54.8 Example 3-15 Resist composition 19100° C. — — 120° C. SA-7 S-15 37.0 55.3 Example 3-16 Resist composition20  90° C. — —  90° C. SA-7 S-16 37.3 55.2 Example 3-17 Resistcomposition 21 120° C. — — 120° C. SA-7 S-11 36.7 53.2 Example 3-18Resist composition 22 110° C. — —  90° C. S-17 S-12 39.3 54.9 Example3-19 Resist composition 16 100° C. — — 120° C. S-18 S-13 39.5 55.1Example 3-20 Resist composition 17  90° C. — —  90° C. S-19 S-14 38.354.8 Example 3-21 Resist composition 14 120° C. — — 120° C. S-17 SA-939.4 60.4 Example 3-22 Resist composition 19 110° C. — —  90° C. S-18SA-9 39.2 62.0 Example 3-23 Resist composition 20 100° C. — — 120° C.S-19 SA-9 38.5 62.4 Example 3-24 Resist composition 20 100° C. T-1  90°C.  90° C. SA-8 S-1 38.6 59.8 Example 3-25 Resist composition 20 100° C.T-2 120° C.  90° C. SA-8 S-1 37.6 57.7 Example 3-26 Resist composition20 100° C. T-3  90° C.  90° C. SA-7 S-1 46.6 56.5 Example 3-27 Resistcomposition 20 100° C. T-4 120° C.  90° C. SA-7 S-1 42.9 62.5 Example3-28 Resist composition 20 100° C. T-5 120° C.  90° C. SA-8 S-1 46.555.1 Example 3-29 Resist composition 20 100° C. T-6  90° C.  90° C. SA-8S-1 36.4 58.3 Example 3-30 Resist composition 20 100° C. T-7 120° C. 90° C. SA-8 S-1 38.9 54.7 Example 3-31 Resist composition 20 100° C.T-8  90° C.  90° C. SA-7 S-1 38.7 56.4 Example 3-32 Resist composition24 120° C. — — 105° C. SA-1 S-8 38.7 56.9 Example 3-33 Resistcomposition 24 120° C. T-3 105° C. 105° C. SA-1 S-9 37.7 54.7 Example3-34 Resist composition 20 100° C. T-9 120° C.  95° C. SA-7 S-1 40.356.2 Example 3-35 Resist composition 24 120° C. T-9  90° C. 105° C. SA-1S-9 37.2 52.0 Comparative Resist composition 17  90° C. 120° C. SA-8SA-9 50.6 72.4 Example 3-1 Comparative Resist composition 16 100° C. 90° C. SA-8 SA-3 54.1 65.9 Example 3-2 Comparative Resist composition15 110° C. 120° C. SA-8 SA-4 53.9 64.3 Example 3-3 Comparative Resistcomposition 14 120° C.  90° C. SA-8 SA-6 52.1 71.0 Example 3-4Comparative Resist composition 17  90° C. 120° C. SA-1 SA-6 50.8 73.0Example 3-5 Comparative Resist composition 16 100° C.  90° C. SA-2 SA-952.5 70.1 Example3-6 Comparative Resist composition 15 110° C. I20° C.SA-5 SA-9 52.1 75.5 Example 3-7

6. KrF Exposure Evaluation (Examples 4-1 to 4-23, and ComparativeExamples 4-1 to 4-8)

Using the resist composition described in Table 5, a resist pattern wasformed through the following operation.

[Application and Post-Application Baking (PB) of Resist Composition]

An organic film DUV42 (manufactured by Brewer Science, Inc.) was appliedonto a 12-inch silicon wafer, and baked at 200° C. for 60 seconds toform an organic film having a film thickness of 100 nm. The resistcomposition prepared in Table 5 was applied thereonto and baked for 60seconds at 100° C. to form a resist film having a film thickness of 200nm.

[Exposure]

The wafer manufactured above was subjected to pattern exposure under theexposure conditions of NA=0.68 and σ=0.60, using a KrF excimer laserscanner (manufactured by ASML, PAS5500/850C, wavelength of 248 nm).Specifically, exposure was carried out so as to form a pattern withline:space=1:1 (L/S pattern) having a line width of 200 nm.Incidentally, the irradiation energy during the resolution of thepattern with line:space=1:1 (L/S pattern) having a line width of 200 nmwas defined as a sensitivity (Eop), and also taken as a sensitivity inthe IL pattern and IS pattern evaluations which will be described later.

[Post-Exposure Baking (PEB)]

After the irradiation, the film was taken out from the KrF exposuredevice, and immediately baked for 60 seconds under the condition of 100°C.

[Development]

Thereafter, the film was immersed in a developer (23° C.) for 60seconds, and then subjected to a rinsing treatment with a rinsing liquidfor 30 seconds.

[Evaluation Test]

Evaluation of the resist pattern was carried out by the followingmethod. Details of the results are shown in Table 12.

(IL Pattern Evaluation)

The irradiation energy during the resolution of the pattern withline:space=1:1 having a line width of 200 nm was defined as asensitivity (Eop), and the limiting resolving power (a minimum linewidth which a line and a space are separated resolved) of the IL pattern(line:space=1:>100) at the Eop was determined. Further, this value wasdefined as “the resolving power (nm) of an IL pattern (isolated linepattern)”. A smaller value thereof indicates better pattern collapseperformance.

(IS Pattern Evaluation)

The irradiation energy during the resolution of the pattern withline:space=1:1 having a line width of 200 nm was defined as asensitivity (Eop), and the limiting resolving power (a minimum linewidth which a line and a space are separated resolved) of the IS pattern(line:space=>100:1) at the Eop was determined. Further, this value wasdefined as “the resolving power (nm) of an IS pattern (isolated spacepattern)”. A smaller value thereof indicates better performance.

TABLE 12 IL IS resolving resolving Devel- power power opment Rinsing(nm) (nm) Example 4-1 Resist composition 1 SA-8 S-1 99.9 84.6 Example4-2 Resist composition 2 S-17 SA-9 101.5 80.3 Example 4-3 Resistcomposition 3 SA-8 S-3 103.6 83.2 Example 4-4 Resist composition 4 SA-7S-4 104.5 79.6 Example 4-5 Resist composition 5 SA-1 S-5 96.5 78.8Example 4-6 Resist composition 6 SA-7 S-6 100.8 75.6 Example 4-7 Resistcomposition 7 SA-8 S-7 99.2 81.3 Example 4-8 Resist composition 8 SA-7S-8 98.7 77.6 Example 4-9 Resist composition 9 SA-8 S-9 102.3 79.6Example 4-10 Resist composition 10 SA-1 S-10 97.2 81.6 Example 4-11Resist composition 11 SA-8 S-11 100.6 83.3 Example 4-12 Resistcomposition 12 SA-7 S-12 99.6 77.7 Example 4-13 Resist composition 22SA-8 S-13 103.5 76.6 Example 4-14 Resist composition 23 SA-7 S-14 95.680.5 Example 4-15 Resist composition 24 SA-1 S-17 96.2 80.6 Example 4-16Resist composition 25 SA-7 S-18 98.3 77.8 Example 4-17 Resistcomposition 31 SA-8 S-19 100.4 79.5 Example 4-18 Resist composition 32SA-7 S-20 100.9 76.2 Example 4-19 Resist composition 33 SA-8 S-2 98.776.5 Example 4-20 Resist composition 26 SA-1 S-10 98.2 81.6 Example 4-21Resist composition 27 SA-8 S-11 100.6 84.3 Example 4-22 Resistcomposition 28 SA-7 S-12 100.6 77.7 Example 4-23 Resist composition 29SA-8 S-13 103.5 75.6 Comparative Example 4-1 Resist composition 1 SA-8SA-9 110.9 101.1 Comparative Example 4-2 Resist composition 1 SA-8 SA-3111.6 106.7 Comparative Example 4-3 Resist composition 1 SA-1 SA-6 113.6108.6 Comparative Example 4-4 Resist composition 1 SA-5 SA-9 112.8 103.2Comparative Example 4-5 Resist composition 26 SA-8 SA-9 109.9 101Comparative Example 4-6 Resist composition 27 SA-8 SA-3 110.6 106.4Comparative Example 4-7 Resist composition 28 SA-1 SA-6 113.1 106.6Comparative Example 4-8 Resist composition 29 SA-5 SA-9 112.2 101.2

7. Evaluation Results

As shown in each of Examples in Tables 9 to 11, it could be seen that incases where any of the exposure light sources are used, the use of atleast one treatment liquid of the developer or the rinsing liquid, whichcontains a first organic solvent having a relative dielectric constantof 4.0 or less and a second organic solvent having a relative dielectricconstant of 6.0 or more, makes it possible to simultaneously suppressthe occurrence of pattern collapse in a resist L/S pattern and theoccurrence of omission failure in a resist C/H pattern.

On the other hand, as clearly seen from Comparative Examples, it wasfound that in a case where both of the developer and the rinsing liquidare not constituted with the first organic solvent having a relativedielectric constant of 4.0 or less and the second organic solvent havinga relative dielectric constant of 6.0 or more, it is impossible tosimultaneously suppress the occurrence of pattern collapse in a resistL/S pattern and the occurrence of omission failure in a resist C/Hpattern.

In addition, it could be confirmed that in a case where the treatmentliquid which contains the first organic solvent having a relativedielectric constant of 4.0 or less and the second organic solvent havinga relative dielectric constant of 6.0 or more is used as the rinsingliquid, the occurrence of the pattern failure in the C/H pattern canfurther be suppressed.

Moreover, it could be confirmed that the treatment liquid of the presentinvention can be applied to any of a negative tone resist and a positivetone resist.

Furthermore, from the comparison of the respective Examples andComparative Examples of Table 12, it was found that in a case where atleast one treatment liquid of a developer or a rinsing liquid containsthe first organic solvent having a relative dielectric constant of 4.0or less and the second organic solvent having a relative dielectricconstant of 6.0 or more, the resolving power of the isolated pattern isbetter. From these results, it is presumed that in a case of using thetreatment liquid of the present invention, it is difficult for thepattern collapse of the isolated pattern and the omission failure amongthe respective patterns to occur.

Furthermore, in a case where the treatment liquid according to thepresent invention was stored in a FluoroPurePFA composite drum (innersurface in contact with liquid; PFA resin lining) manufactured byEntegris, Inc., and a steel-made drum can manufactured by JFE SteelCorporation (inner surface in contact with liquid; zinc phosphate-coatedfilm) at normal temperature for 14 days, using the method described inJP2014-112176A, and then subjected to analysis of concentrations of wetparticles and organic impurities, and analysis of concentration of metalimpurities were carried out, better results could be obtained from theFluoroPurePFA composite drum manufactured by Entegris, Inc. (innersurface in contact with liquid; PFA resin lining) than from thesteel-made drum can manufactured by JFE Steel Corporation (inner surfacein contact with liquid; zinc phosphate-coated film).

What is claimed is:
 1. A treatment liquid for patterning a resist film,used for subjecting a resist film obtained from an actinic ray-sensitiveor radiation-sensitive resin composition to at least one of developmentor washing, and containing an organic solvent, wherein the treatmentliquid contains a first organic solvent having a relative dielectricconstant of 4.0 or less and a second organic solvent having a relativedielectric constant of 6.0 or more, wherein the first organic solventincludes a hydrocarbon-based solvent, and the hydrocarbon-based solventincludes undecane, and wherein a mass ratio of the first organic solventto the second organic solvent is 60:40 to 90:10.
 2. The treatment liquidaccording to claim 1, wherein the treatment liquid is a rinsing liquid.3. The treatment liquid according to claim 2, wherein the second organicsolvent includes a ketone-based solvent.
 4. The treatment liquidaccording to claim 3, wherein the ketone-based solvent includes anacyclic ketone.
 5. The treatment liquid according to claim 1, whereinthe second organic solvent includes a ketone-based solvent.
 6. Thetreatment liquid according to claim 5, wherein the ketone-based solventincludes an acyclic ketone.
 7. A treatment liquid for patterning aresist film, used for subjecting a resist film obtained from an actinicray-sensitive or radiation-sensitive resin composition to at least oneof development or washing, and containing an organic solvent, whereinthe treatment liquid contains a first organic solvent having a relativedielectric constant of 4.0 or less and a second organic solvent having arelative dielectric constant of 6.0 or more, wherein a mass ratio of thefirst organic solvent to the second organic solvent is 60:40 to 90:10,wherein the second organic solvent includes a ketone-based solvent, andthe ketone-based solvent includes an acyclic ketone, wherein the firstorganic solvent includes a hydrocarbon-based solvent, and wherein thehydrocarbon-based solvent includes undecane.
 8. A treatment liquid forpatterning a resist film, used for subjecting a resist film obtainedfrom an actinic ray-sensitive or radiation-sensitive resin compositionto at least one of development or washing, and containing an organicsolvent, wherein the treatment liquid contains a first organic solventhaving a relative dielectric constant of 4.0 or less and a secondorganic solvent having a relative dielectric constant of 6.0 or more,wherein the first organic solvent includes a hydrocarbon-based solvent,and the hydrocarbon-based solvent includes undecane, and wherein a massratio of the first organic solvent to the second organic solvent is80:20 to 90:10.
 9. A pattern forming method comprising: a resist filmforming step of forming a resist film using an actinic ray-sensitive orradiation-sensitive resin composition; an exposing step of exposing theresist film; and a treating step of treating the exposed resist filmwith the treatment liquid according to claim
 1. 10. A pattern formingmethod comprising: a resist film forming step of forming a resist filmusing an actinic ray-sensitive or radiation-sensitive resin composition;an exposing step of exposing the resist film; and a treating step oftreating the exposed resist film with the treatment liquid according toclaim 1, wherein the treating step includes: a developing step ofcarrying out development with a developer; and a rinsing step ofcarrying out washing with a rinsing liquid, and the rinsing liquid isthe treatment liquid.